Co-processing hydrothermal liquefaction oil and co-feed to produce biofuels

ABSTRACT

The present disclosure relates to processes for producing biofuel compositions by processing hydrocarbon co-feed and a bio-oil obtained via hydrothermal liquifaction (HTL) of a cellulosic biomass to form an HTL oil. The cellulosic mass can be processed at an operating temperature of about 425° C. or less and an operating pressure of about 200 atm or less. The HTL oil is co-processed with a hydrocarbon co-feed (e.g., petroleum fraction) in a cracking unit, such as an FCC unit, a coker unit or a visbreaking unit, in the presence of a catalyst to produce a cracked product (biofuel). The bio content of the cracked product provides RIN credits for the cracked product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/735,919 filed Sep. 25, 2018, which is herein incorporated byreference in its entirety.

FIELD

The present disclosure relates to processes for producing biofuelcompositions wherein a hydrocarbon (petroleum) oil and a hydrothermalliquefaction (HTL) oil(s) are co-processed in a cracking unit. Inparticular, the disclosure is directed to processes for producing fuelcompositions comprising cracking a mixture of hydrocarbon co-feed and anHTL oil derived from cellulose.

BACKGROUND

With the rising costs and environmental aspects associated with fossilfuels, renewable energy sources have become increasingly important. Thedevelopment of renewable fuel sources provides a means for reducing thedependence on fossil fuels. Accordingly, many different areas ofrenewable fuel research are currently being explored and developed.

To encourage such research efforts, Congress created the renewable fuelstandard (also referred to as “RFS”) program to reduce greenhouse gasemissions and expand the nation's renewable fuels sector while reducingreliance on imported oil. This program was authorized under the EnergyPolicy Act of 2005 and expanded under the Energy Independence andSecurity Act of 2007. Examples of such legislation include, but are notlimited to, the United States Environmental Protection Agency (alsoreferred to as “EPA”), the Energy Independence and Security Act (alsoreferred to as “EISA”) and California AB 32—Global Warming SolutionsAct, which respectively established an RFS and a Low Carbon FuelStandard (also referred to as “LCFS”). For instance, under EISA, themandated annual targets of renewable content in fuel are implementedthrough an RFS that uses tradable credits (called RenewableIdentification Numbers, referred to herein as “RINs”) to trail andconduct the production, distribution and use of renewable fuels fortransportation or other purposes (e.g., pharmaceutical, plastics/resins,etc.). Targets under the LCFS can be met by trading of credits generatedfrom the use of fuels with a lower greenhouse gas emission value thanthe gasoline baseline. Among such regulations, there are some related tothe use of cellulosic containing biomass (cellulosic biomass) that canearn Cellulosic Renewable Identification Numbers (also referred to as“C-RINs”). The use of cellulosic biomass can also support fuel producersin meeting their Renewable Volume Obligations (also referred to as“RVO”).

With its low cost and wide availability, biomass has increasingly beenemphasized as an ideal feedstock in renewable fuel research.Consequently, many different conversion processes have been developedthat use biomass as a feedstock to produce useful biofuels and/orspecialty chemicals. Existing biomass conversion processes include, forexample, combustion, gasification, slow pyrolysis, fast pyrolysis,liquefaction, and enzymatic conversion. One of the useful products thatmay be derived from the aforementioned biomass conversion processes is aliquid product commonly referred to as “bio-oil.” Bio-oil may beprocessed into transportation fuels, hydrocarbon chemicals, and/orspecialty chemicals.

Despite recent advancements in biomass conversion processes, many of theexisting biomass conversion processes produce low-quality bio-oils thatare highly unstable and often contain high amounts of oxygen. Thesebio-oils require extensive secondary upgrading in order to be utilizedas transportation fuels and/or as fuel additives due their instability.Furthermore, the transportation fuels and/or fuel additives derived frombio-oil vary in quality depending on factors affecting the stability ofthe bio-oil, such as the original oxygen content of the bio-oil.

Bio-oils can be subjected to various upgrading processes in order toprocess the bio-oil into renewable fuels and/or fuel additives. However,prior upgrading processes have been relatively inefficient and producerenewable fuels and/or fuel additives that have limited use in today'smarket. Furthermore, only limited amounts of these bio-oil derivedtransportation fuels and/or fuel additives may be combinable withpetroleum-derived gasoline or diesel.

Accordingly, there is a need for improved processes and systems forproducing and using bio-oils to produce renewable fuels.

References for citing in an Information Disclosure Statement (37 CFR1.97(h)): U.S. Pat. No. 9,120,989; U.S. 2013/0118059.

SUMMARY

The present disclosure relates to processes for producing biofuelcompositions by processing hydrocarbon co-feed and a bio-oil obtainedvia hydrothermal liquifaction (HTL) of a cellulosic biomass to form anHTL oil. The cellulosic mass can be processed at an operatingtemperature of about 425° C. or less, an operating pressure of about 200atm or less, a residency time of about 5 minutes to about 60 minutes, inthe presence of a catalyst. The HTL oil is co-processed with ahydrocarbon co-feed (e.g., petroleum fraction) in a cracking unit, suchas an FCC unit, a coker unit or a visbreaking unit, in the presence of acatalyst, at an operating temperature of about 400° C. to about 700° C.,such as about 545° C. to about 585° C., an operating pressure of about10 psig to about 50 psig, such as about 15 psig (1 bar) to about 30 psig(2 bar), and/or a residency time of about 1 second to about 30 seconds,such as about 2 seconds to about 10 seconds to produce a biofuel.

In an embodiment, a process for generation of biofuels includesintroducing (“feeding”) through separate injection nozzles, an HTL oiland a hydrocarbon (such as Vaccum Gas Oil (VGO) and/orResid/De-Asphalted Oil (DAO) to a cracker, such as a fluidized catalyticcracking (FCC) unit.

In at least one embodiment, the present disclosure provides a method ofprocessing a hydrocarbon co-feed (e.g., VGO) with an HTL oil in thepresence of a cracking catalyst resulting in an improved biofuelproduct.

In at least one embodiment, a method of preparing a biofuel includes: i)processing a hydrocarbon co-feed with a HTL oil feedstock in thepresence of a cracking catalyst; and ii) optionally, adjusting feedaddition rates of the hydrocarbon co-feed, the HTL oil feedstock, orboth, to target a desirable biofuel product profile, a risertemperature, or a reaction zone temperature; or iii) optionally,adjusting the amount of cracking catalyst to combined hydrocarbonco-feed/HTL oil ratio (catalyst : oil(s) ratio).

Further, the present disclosure provides a cracking system wherein theoils are injected separately into the cracker unit so that separation ofthe final biofuel is not required. For example, the system can includeat least two or more feed nozzles coupled with a cracking unit forinjection of the oils into the cracking unit.

DETAILED DESCRIPTION

The present disclosure relates to methods of generating biofuels byco-processing an HTL oil, derived from a cellulosic biomass, with ahydrocarbon oil in a cracking unit. The HTL oil can be derived fromcellulosic biomass processed at an operating temperature of about 425°C. or less, an operating pressure of about 200 atm or less, a prolongedresidency time of about 5 minutes to about 60 minutes, in the presenceof a catalyst to form an HTL oil. The HTL oil is co-processed with ahydrocarbon oil (e.g., petroleum fraction) in the presence of a crackingcatalyst in cracking unit at an operating temperature of about 400° C.to about 700° C., such as about 545° C. to about 585° C., an operatingpressure of about 10 psig to about 50 psig, such as about 15 psig (1bar) to about 30 psig (2 bar), and/or a residency time of about 1 secondto about 30 seconds, such as about 2 seconds to about 10 seconds, toform a biofuel which may be a cellulosic-renewable identificationnumber-compliant fuel. Processes of the present disclosure providebiofuel compositions without any separation process of the crackedproduct(s). The cracking process can be performed using a system of atleast two or more injection nozzles on the cracking unit, which promotesbetter blending of the HTL and hydrocarbon oils (and ultimately crackedproduct(s)) by increasing the dispersion, providing additional time-,energy- and cost-efficiency. In an embodiment, a process for generationof biofuel oils is described that includes introducing (“feeding”),separately or as a mixture, HTL oil and hydrocarbon (such as Vaccum GasOil (VGO) and/or Resid/De-Asphalted Oil (DAO) to a cracking unit such asa fluidized catalytic cracking (FCC) unit, such that a portion of thefeed HTL oil passes through the FCC (or alternate cracking process likecoking or visbreaking) reactor section (with some conversion) and endsup in the product fuel. The bio content of the cracked product providesRIN credits for the cracked product.

It has been discovered that when HTL oil is the source of the bio-oiland is processed along with a hydrocarbon oil, and the two oils areseparately injected into the cracking unit, a useful biofuel is produceddirectly and a separation step is not required to obtain the biofuel.The present disclosure is directed to a simple, time-effective,energy-effective, and cost-effective environmentally-friendly processthat combines HTL technology and cracking technology for conversion ofoils into biofuels. In at least one embodiment, the present disclosureadvantageously provides a process for meeting renewable fuel targets ormandates established by governments, including legislation andregulations for transportation fuel sold or introduced into commerce inthe United States.

In at least one embodiment, the present disclosure provides a method ofprocessing a hydrocarbon co-feed (e.g., VGO) with a portion thereofblended with an amount of HTL oil. The feeds are processed in thepresence of a cracking catalyst resulting in an improved yield of thebiogenic carbon, such as an increase of at least 0.5 wt %, such as fromabout 0.5 wt % to 3 wt %, thus relative to the identical process on anequivalent energy or carbon content basis of the feedstream where thehydrocarbon co-feed is not blended with any other fuel feedstock (suchas a HTL oil).

In at least one embodiment, a method of preparing a biofuel includes: i)processing a hydrocarbon feedstock with an HTL feedstock in the presenceof a catalyst; and ii) optionally, adjusting feed addition rates of thehydrocarbon co-feed, the HTL feedstock, or both, to target a desirablebiofuel product profile, a riser temperature, or a reaction zonetemperature; or iii) optionally, adjusting the cracking catalyst tocombined hydrocarbon/HTL feedstock ratio (catalyst:oil(s) ratio).

Further, the present disclosure provides a system for separatelyinjecting the feedstocks into the cracking unit, for example, byproviding at least two or more feed nozzles coupled with an FCC unit forinjection into the FCC unit.

Methods and systems for making compositions of the present disclosuremay include renewable fuel (also referred to as HTL oil or renewableoil) as a feedstock in cracking units, such as FCCs, and other refinerysystems or field upgrader operations. Renewable fuels may include fuelsproduced from renewable resources. Suitable HTL oils may includebiofuels such as solid biofuels (e.g., wood used as fuel, cellulosicbiomass), biodiesel, bio-alcohols (e.g., biomethanol, bio-ethanol,biobutanol) from biomass, and hydrogen fuel (when produced withrenewable energy sources), catalytically converted biomass to liquids,and thermochemically produced liquids. In at least one embodiment, theHTL oil is a cellulosic material from biomass.

As used herein, and unless otherwise specified, the term “Ce” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n. Additionally, the hydrocarboncompound may contain, for example, heteroatoms such as sulphur, oxygen,nitrogen, or any combination thereof. Suitable hydrocarbon compounds mayinclude acetic acid, formic acid, levulinic acid and gamma-valerolactoneand/or mixtures thereof.

The term “hydrocarbon co-feed” refers to a co-feed that contains one ormore hydrocarbon compounds.

The term “fluid hydrocarbon co-feed” refers to a hydrocarbon feed thatis not in a solid state. The fluid hydrocarbon co-feed can be a liquidhydrocarbon co-feed, a gaseous hydrocarbon co-feed, or a mixturethereof. Also, the fluid hydrocarbon co-feed can be fed to a catalyticcracking reactor in a liquid state, and/or in a gaseous state, or in apartially liquid-partially gaseous state. When injected into thecatalytic cracking reactor in a liquid state, and/or in a gaseous state,or in a partially liquid-partially gaseous state, the fluid hydrocarbonco-feed may be vaporized upon entry, such as the fluid hydrocarbonco-feed may be contacted in the gaseous state with the FCC catalyst. Ahydrocarbon co-feed can be a petroleum oil.

The term “liquefaction”, also referred to as “liquefying”, refers to theconversion of a gas material and/or solid material, such as cellulosicmaterial, into one or more liquid (liquefied) products.

The term “liquefied product” refers to a product that is liquid at atemperature of about 20° C. and a pressure of about 1 bar absolute (0.1MPa). A “liquefied product” can also refer to a product that can beconverted into a liquid by melting (e.g., melting upon heat) ordissolving in a solvent (e.g., an organic solvent). In at least oneembodiment, the liquefied product is a liquefied product that is liquidat a temperature of about 80° C. and a pressure of about 1 bar absolute(0.1 MPa). Suitable liquefied products may be more or less viscous andwith a viscosity that may extensively vary.

The term “liquid solvent” is herein understood to be a solvent that isliquid at the temperature and pressure at which the liquefaction processis carried out.

The term “final liquefied product” refers to a liquefied productsuitable to be directed to the catalytic cracking process.

The term “cracked product(s)” refers to product(s) obtained afterprocessing/cracking/breaking down heavy hydrocarbon molecules (usuallynonvolatile) into lighter molecules (such as light oils (correspondingto gasoline), middle-range oils used in diesel fuel, residual heavyoils, a solid carbonaceous product known as coke, and such gases asmethane, ethane, ethylene, propane, propylene, and butylene) by means ofheat, pressure, and/or catalysts in a refinery reactor unit, such as anFCC reactor unit. The terms “cracked product” and “final liquefiedRINs-product” may be used herein interchangeably.

The term “visbreaking” refers to the untangling of molecules in fluidduring heat treatment and/or to the breaking of large molecules intosmaller molecules during heat treatment, which results in a reduction ofthe viscosity of the fluid.

Hydrothermal Liquefaction

Hydrothermal liquefaction (HTL) technology produces HTL oil at a lowertemperature with much longer residency time as compared to, for example,a fast py-oil process. The HTL process, also called “hydrous pyrolysis”,is used for the reduction of complex organic materials such as biowasteand/or biomass into crude oil and other chemicals. The pathway of HTLcan include three major phases, i) depolymerisation, followed by ii)decomposition and iii) recombination/repolymerisation of the reactivefragments. HTL can involve direct liquefaction of biomass, with thepresence of water and perhaps some catalysts, to directly convertbiomass into liquid oil, at a reaction temperature of less than 400° C.HTL can have different pathways for the biomass feedstock and, unlikebiological treatment (e.g., anaerobic digestion), HTL converts feedstockinto oil rather than gases or alcohol. There are some unique features ofthe HTL process and its product compared with other biologicalprocesses: 1) the end product is a crude oil (which has much higherenergy content of fuels than syngas or alcohol, the energy content beingan important property of fuels obtained by the amount of heat producedby the burning of 1 gram of a substance, and is measured in joules pergram); 2) if the feedstock contains a lot of water, HTL does not requiredrying. As noted above, known processes require extensive separation ofproducts after co-processing in the cracking unit which requireshigh-energy consumption by large separators, which counteracts the lowergreenhouse gas emissions that the obtained biofuels are aiming toachieve. An HTL process of the present disclosure can be performed inany suitable HTL reactor, such as described in U.S. Pat. Pub. No.2013/0118059, incorporated by reference.

Suitable biomass, biomass materials, or biomass components, include butare not limited to, wood, wood residues, forest debris, sawdust, slashbark, scrap lumber, manure, thinnings, forest cullings, begasse, cornfiber, corn stover, empty fruit bunches, fronds, palm fronds, flax,straw, low-ash straw, energy crops, palm oil, non-food-based biomassmaterials, crop residue, slash, pre-commercial thinnings, urban wood andyard wastes, tree residue, annual covercrops, switchgrass, millresidues, miscanthus, animal manure (dry and/or wet), cellulosiccontaining components, cellulosic components of separated yard waste,cellulosic components of separated food waste, cellulosic components ofseparated municipal solid waste, or combinations thereof. Suitablecellulosic biomass may include biomass derived from or containingcellulosic materials. For purposes of the present disclosure, the HTLoil can be an oil processed from a cellulosic-containing biomass.

The biomass can be characterized as being compliant with U.S. renewablefuel standard program (RFS) regulations, or a biomass suitable forpreparing a cellulosic-renewable identification number-compliant fuel,for example. Suitable biomass can be characterized as being compliantwith those biomass materials specified in the pathways for a D-code 1,2, 3, 4, 5, 6, or 7-compliant fuel, in accordance with the U.S.renewable fuel standard program (RFS) regulations, such as the biomasscan be characterized as being compliant with those biomass materialssuitable for preparing a D-code 3 or 7-compliant fuel, in accordancewith the U.S. renewable fuel standard program (RFS) regulations or thebiomass can be characterized as being composed of only hydrocarbons (orrenewable hydrocarbon biofuels, also called “green” hydrocarbons).

The term “renewable fuel oil” (also referred to as “HTL oil”) refers toa biomass-derived fuel oil or a fuel oil produced from the conversion ofbiomass. The HTL oil used in the process of the present disclosure is acellulosic renewable fuel oil (also referred to as “cellulosic HTLoil”), and may be derived or prepared from the conversion ofcellulosic-containing biomass which is processed via HTL to produce anHTL oil. The HTL-processed HTL oil described herein could also beblended with various non-hydrodeoxygenated, non-deoxygenated,non-hydrotreated, non-upgraded, non-catalytically processed,thermo-mechanically-processed, HTL-processed HTL oil and/or othernon-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded,non-catalytically processed, thermo-mechanically-processed,HTL-processed HTL oil that has been derived from other biomass to formblends of non-hydrodeoxygenated, non-deoxygenated, non-hydrotreated,non-upgraded, non-catalytically processed,thermo-mechanically-processed, HTL-process HTL oil.

In at least one embodiment, the HTL oil is a liquid formed from abiomass including a cellulosic material, wherein the only processing ofthe biomass is a thermo-mechanical process (specifically includinggrinding and slow thermal processing (e.g., HTL process), and optionallypost-processing or enrichment of the HTL oil liquid prior tointroduction into a hydrocarbon conversion unit.

In particular, the process for making cellulosic RIN-compliant fuelcompositions may include a liquefaction process where a cellulosicmaterial is contacted with a liquid solvent to produce a final HTL oilliquefied product. This process may also be referred to as liquefactionor liquefying of the cellulosic material. The liquefaction or liquefyingmay be carried out by means of a liquefaction or liquefying reaction.

In at least one embodiment, the liquefaction process is a hydrothermalliquefaction process, meaning that the pyrolysis of a biomass may occurat a reacting (e.g., operating) temperature of less than about 425° C.,such as from about 200° C. to 425° C., such as from about 250° C. to350° C., and at a residence time of at least 1 minute, such as fromabout 1 minute to about 2 hours, such as from about 5 minutes to about1.5 hours, such as from about 10 minutes to about 1 hour, such as fromabout 15 minutes to about 45 minutes, such as from about 20 minutes toabout 30 minutes.

A cellulosic material can refer to a material containing cellulose. Inat least one embodiment, the cellulosic material is a lignocellulosicmaterial. A lignocellulosic material includes lignin, cellulose andoptionally hemicellulose. One of the advantages of the liquefactionprocess is that the process enables liquefaction not only of thecellulose but also the lignin and hemicelluloses.

For the purposes of this disclosure, any suitable cellulose-containingmaterial can be used as cellulosic material. The cellulosic material foruse according to the present disclosure may be obtained from a varietyof plants and plant materials including forestry wastes, agriculturalwastes, sugar processing residues and/or mixtures thereof. Examples ofsuitable cellulose-containing materials include, but are not limited to,agricultural wastes such as corn cobs, corn stover, soybean stover, ricestraw, rice hulls, oat hulls, corn fibre, cereal straws such as wheat,barley, rye and oat straw; grasses; forestry products such as wood andwood-related materials such as sawdust; waste paper; sugar processingresidues such as bagasse and beet pulp; or mixtures thereof.

The HTL oil formed by liquefaction can be an unenriched liquid (such asan unenriched HTL oil) formed from ground-up biomass by a process, suchas a slow thermal processing, wherein the resulting liquid may be atleast 50 wt %, such as at least 60 wt %, such as at least 70 wt %, suchas at least 75 wt %, such as at 80 wt %, such as at least 85 wt %, suchas at least 90 wt % of the total weight of the processed biomass.Namely, the liquid (i.e., the HTL oil) yield from the processed biomasscan be at least 50 wt %, such as at least 60 wt %, such as at least 70wt %, such as at least 75 wt %, such as at least 80 wt %, such as atleast 85 wt %, such as at least 90 wt % of the total weight of theground biomass being processed. The term “unenriched” refers to HTL oilliquid that does not undergo any further pre- or post-processingincluding, more particularly, no hydrodeoxygenation, no hydrotreating,no catalytic exposure or contact. For example, unenriched HTL oil can beprepared from the ground biomass and then transported and/or stored, andcan be even heated or maintained at a given temperature; not exceedingabout 65° C., on its way to being introduced into the conversion unit atthe refinery (i.e., refinery FCC unit). The mechanical handlingassociated with transporting, storing, heating, and/or pre-heating ofthe unenriched HTL oil should not be considered an enriching process. Anunenriched HTL oil may include one or more unenriched HTL oils mixedfrom separate unenriched assortments and/or unenriched assortmentsgenerated from different cellulosic biomass (such as assorted varietiesof non-food biomass). Additionally, mixed compositions can be blended topurposefully provide or achieve particular characteristics in thecombined unenriched HTL oil.

In at least one embodiment, the HTL oil includes thermally convertedbiomass or thermo-mechanically converted biomass. Suitable HTL oils mayinclude an HTL liquid (i.e., HTL oil), derived or prepared from theconversion of biomass (e.g., cellulosic biomass). Any suitable HTL oilmay include a non-HDO HTL oil, a non-deoxygenated HTL oil, anon-upgraded HTL oil, a thermally-processed cellulosic HTL oil, athermally-processed, non-upgraded-cellulosic HTL oil, athermally-processed biomass liquid; athermally-processed-non-upgraded-biomass liquid, a thermally processednon-food-based biomass liquid, a thermally-processed non-food,cellulosic-based biomass liquid, a thermally-processednon-food-renewable liquid, a thermally-processed cellulosic liquid, aslow thermal-processed cellulosic liquid, a slow thermal-processedbio-oil, a slow thermal processed biomass liquid or thermo-pyrolyticliquid having less than 5 wt % solid content, such as less than 5 wt %,such as less than 4 wt %, such as less than 3 wt %, such as less than 2wt %, such as less than 1 wt %, such as less than 0.5 wt % solidcontent. Further examples of suitable HTL oil may include a conditionedHTL oil, a non-hydrotreated-non-upgraded HTL oil, a HTL oil or HTLliquid, a thermo-HTL oil or a thermo-HTL liquid, a bio-oil or a bio-oilliquid, a biocrude oil or biocrude liquid, a thermo-catalytic HTL oil ora thermo-catalytic HTL liquid, a catalytic HTL oil or a catalytic HTLliquid, or any combinations thereof.

In at least one embodiment, the HTL oil may include one or more of anon-HDO HTL oil, a non-deoxygenated HTL oil, a non-upgraded HTL oil, athermally-processed cellulosic HTL oil, a slowthermo-mechanically-processed HTL oil, a non-hydrotreated-non-upgradedHTL oil, an HTL oil or HTL liquid; or a thermo-HTL oil or a thermo-HTLliquid.

Moreover, the liquefaction process may include torrefaction, steamexplosion, particle size reduction, densification and/or pelletizationof the cellulosic material before the cellulosic material is contactedwith the liquid solvent. Such torrefaction, steam explosion, particlesize reduction, densification and/or pelletization of the cellulosicmaterial may advantageously allow for improved process operability andeconomics.

For example, the cellulosic material can be processed into smallparticles before being used in the process of the present disclosure,thus in order to promote liquefaction. In at least one embodiment, thecellulosic material is processed into particles having a particle sizedistribution with an average particle size of about 0.01 millimeter orgreater, such as of about 0.05 millimeter or greater, such as of about0.1 millimeter or greater, such as of about 0.5 millimeter or greater,such as from about 0.01 millimeter to about 30 centimeters, such as fromabout 1 millimeter to about 20 centimeters, such as from about 2millimeter to about 10 centimeters, such as from about 5 millimeter toabout 5 centimeters. For practical purposes of the present disclosure,the particle size of the cellulosic material in the centimeter andmillimeter range can be determined by sieving.

Particularly, the cellulosic material can be a lignocellulosic materialthat may involve a pre-treatment in order to remove and/or degradeundesirable lignin and/or hemicellulose. Suitable pre-treatments oflignocellulosic material may include fractionation, pulping andtorrefaction processes.

Suitable HTL oils may have a pH in the range of about 0.5 to about 8,such as of 0.5 to 7, such as of about 0.5 to about 6.5, such as of about1 to about 6, such as of about 1.5 to about 5, such as of about 1.5 to4, such as of about 2 to about 3.5. In at least one embodiment, the pHof the HTL oil is less than 8, such as less than 7, such as less than6.5, such as less than 6, such as less than 5.5, such as less than 5,such as less than 4.5, such as less than 4, such as less than 3.5, suchas less than 3, less than 2.5, such as about 2. For example, the pH ofthe HTL oil may be altered or modified by the addition of an external,non-biomass derived material or pH altering agent. For example, the HTLoil may be acidic. Since the HTL oil is injected in a small quantityinto the FCC (as compared to the total weight of the processed biofuelcomposition), it has been discovered that the risk of corrosion from theacidity generated during the process is limited and the conversionprocess of hydrocarbons to biofuel in the FCC provides desirable biofuelcompositions at pH values of about 5 to 7. Also, the HTL oil may havethe pH resulting from the conversion of the biomass from which it may bederived, such as a biomass-derived pH.

In at least one embodiment, the HTL oil has a solids content from about0.002 wt % to about 10 wt %, such as from about 0.005 wt % to about 8 wt%, such as from about 0.01 wt % to about 6 wt %, such as from about 0.05wt % to about 4 wt %, such as from about 0.1 wt % to about 3 wt %, suchas from about 0.2 wt % to about 2 wt %, such as from about 0.5 wt % toabout 1 wt %, based on the total weight of the HTL oil.

The term “liquid solvent” refers to a solvent that is liquid at apressure of about 1 bar atmosphere (0.1 MPa) and at a temperature ofabout 80° C. or higher, such as about 90° C. or higher, such as about100° C. or higher, such as about 120° C. In at least one embodiment, theliquid solvent includes or is water.

In at least one embodiment, the liquid solvent includes or is an organicsolvent. Suitable organic solvent can be a solvent including one or morehydrocarbon compounds. Under standard environmental conditions,hydrocarbon compounds are nonpolar hydrophobic.

Suitable HTL oil may include a solvent content of from 5 wt % to 45 wt%, such as from 10 wt % to 35 wt %, such as from 15 wt % to 30 wt %,such as from 20 wt % to 35 wt %, such as alternatively 20 wt % to 30 wt%, such as alternatively 30 wt % to 35 wt %, such as alternatively 25 wt% to 30 wt % water.

In at least one embodiment, the HTL oil includes an oxygen content levelhigher than that of a hydrocarbon co-feed. For example, the HTL oil mayhave an oxygen content level of greater than 10 wt %, on a dry basis,such as an oxygen content level in the range of about 10 wt % to 50 wt%, such as from about 15 wt % to about 40 wt %, such as from about 20 wt% to about 35 wt %, on a dry basis.

For example, the HTL oil may include a carbon content of about 30 wt %to 90 wt %, such as of about 35 wt % to 80 wt %, such as of about 40 wt% to 70 wt %, such as of about 50 wt % to 60 wt %, and/or an oxygencontent of about 20 wt % to 50 wt % oxygen content, such as of about 30wt % to 40 wt % oxygen content, on a dry basis.

In at least one embodiment, the HTL oil includes a carbon content of atleast 35 wt % of the carbon content contained in the biomass from whichit may be derived. For instance, the HTL oil may include a carboncontent level of from about 35 wt % to about 100 wt %, such as about 40wt % to about 90 wt %, such as about 45 wt % to about 80 wt %, such asabout 50 wt % to about 70 wt %, such as about 55 wt % to about 60 wt %,of the carbon content contained in the biomass from which it may bederived. In at least one embodiment, the HTL oil includes a carboncontent level lower than that of a hydrocarbon co-feed. For example, theHTL oil may include a carbon content of from about 30 wt % to about 90wt %, such as about 40 wt % to 80 wt %, such as from 50 wt % to about 60wt %, on a dry basis.

The energy content is a property of fuels and is defined as the fuel'sprimary energy obtained by the amount of heat produced by the burning of1 gram of a substance, and is measured in joules per gram. The energycontent of a fuel is determined by burning an amount of the fuel andcapturing the heat released in a known mass of water in a calorimeter.The energy released can be calculated at initial and final temperaturesusing the equation

H=Δt·m·Cp

where H is the heat energy absorbed (in Joules), At is the change intemperature (in ° C.), m is the mass (in gram), and Cp is the specificheat capacity (4.18 J/g° C. for water). Dividing the resulting energyvalue by grams of biomass burned gives the energy content (in J/g). TheHTL oil may include an energy content level of at least 20% of theenergy content contained in the biomass from which it may be derived,such as an energy content level of about 40% to at least 100% of theenergy content contained in the biomass from which it may be derived. Inat least one embodiment, the HTL oil includes an energy content level ofabout 50% to about 99% of the energy content contained in the biomassfrom which it may be derived, such as from about 55% to 90%, such asfrom about 50% to about 80%, such as from about 60% to about 70%,alternately from about 70% to about 80% of the energy content containedin the biomass from which it may be derived.

In at least one embodiment, a suitable catalyst for HTL processing is analkali reagent. Examples of suitable alkali catalyst for HTL can be, butare not limited to, Na₂CO₃, KOH, K₂CO₃, FeSO₄, Ni(OH)₂.

In at least one embodiment, the organic solvent is partially derivedfrom cellulosic material, such as lignocellulosic material, and/orpartially derived from a hydrocarbon source. The organic solvent mayinclude a mixture of a fraction of a hydrocarbon oil and/or one or morehydrocarbon compounds that may be obtained by acid hydrolysis of acellulosic material, such as a lignocellulosic material.

In at least one embodiment, the organic solvent includes at least one ormore carboxylic acids, for example, such as formic acid, acetic acid,levulinic acid and/or pentanoic acid. Such carboxylic acid(s) can bepresent before beginning the liquefaction process, that is, whichcarboxylic acid(s) cannot be in-situ generated and/or derived from thecellulosic material during the reaction.

The organic solvent may be water-miscible at the reaction temperature ofthe liquefaction process. The liquefaction process may includecontacting the cellulosic material with a solvent mixture including theorganic solvent with or without the presence of water.

During the liquefaction process, water in the solvent mixture may begenerated in-situ. In at least one embodiment, the organic solvent ispresent in an amount of from about 1 wt % to about 99 wt %, such as fromabout 5 wt % to about 95 wt %, such as from about 10 wt % to about 90 wt%, such as from about 15 wt % to about 85 wt %, such as from about 20 wt% to about 80 wt %, such as from about 25 wt % to about 70 wt %, such asfrom about 30 wt % to about 70 wt %, such as from about 40 wt % to about60 wt %, based on the total weight of water and organic solvent.

A cellulosic material and an organic solvent may be mixed in a solventmixture at an organic solvent-to-cellulosic material ratio of 0.5:1 to50:1, such as 1:1 to 40:1, such as 2:1 to 30:1, such as 3:1 to 20:1,such as 4:1 to 15:1, such as 5:1 to 10:1, such as 6:1 to 8:1 by weight.

In at least one embodiment, the liquefaction process is carried out inthe presence of a catalyst. The use of a catalyst advantageously allowsone to lower the reaction temperature and speed up the reaction process.

In at least one embodiment, an HTL process is conducted in an aqueouscondensed phase. The HTL may be conducted at an operating temperature offrom about 200° C. to 425° C., such as from about 250° C. to 400° C.,such as from 275° C. to 375° C., such as from about 300° C. to 350° C.,alternatively from about 250° C. to 350° C. In at least one embodiment,the HTL is conducted at an operating pressure of from about 50 atm toabout 400 atm, such as from about 100 atm to about 300 atm, such as fromabout 150 atm to about 275 atm, such as at 200 atm.

An HTL process may be conducted at a residence time of from about 1minute to about 2 hours, such as from about 5 minutes to about 1 hour,alternatively from about 5 minutes to about 30 minutes. In at least oneembodiment, a processed HTL oil is produced at a carbon yield to biofuelof about 10% to about 60%, such as from about 15% to about 50%, such asfrom about 20% to about 40%. The present disclosure provides a processedHTL oil having a low heating value of about 20 MJ/kg to 60 MJ/kg, suchas about 25 MJ/kg to about 50 MJ/kg.

In at least one embodiment, an HTL oil is produced via HTL with anoxygenates content of about 15% or lower, such as about 12% or lower,such as about 10% or lower, and a water content of about 8% or lower,such as about 5% or lower, such as about 3% or lower. Without beingbound by theory, the low contents of water and oxygenates can promote agreater thermal stability of the HTL oil formed via HTL.

Kinematic Viscosity at 40° C. (KV40) of the HTL oil after HTL can be atleast 500 cSt or greater, such as 1,000 cSt or greater, such as 1,500cSt or greater, such as 2,000 cSt or greater, such as 2,500 cSt orgreater, such as 3,000 cSt or greater, such as 3,500 cSt or greater,such as at least 4,000 cSt or greater.

Fluid Catalytic Cracking

In at least one embodiment, the present disclosure also provides aprocess for conversion of a cellulosic material including: i) aliquefaction process, including contacting a cellulosic material with orwithout an organic solvent at a temperature of from about 200° C. toabout 425° C., optionally in the presence of a catalyst, where theorganic solvent includes a fraction of one or more hydrocarbon oil(s),to produce an HTL oil (e.g., a final liquefied product); ii) a catalyticcracking process, including contacting a mixture of at least part of theHTL oil and the organic solvent (fraction of one or more hydrocarbonoil(s)) with an FCC catalyst in an FCC reactor at a temperature of fromabout 400° C. to about 700° C., such as about 545° C. to about 585° C.,thus to produce one or more cracked product(s). In at least oneembodiment, the final cracked product of stage ii) may suitably be thebiofuel composition or any part thereof. For example, the final crackedproduct of stage ii) can be introduced to (e.g., blended with) one ormore additional components to form a biofuel composition. The finalcracked product, with or without blending to one or more additionalcomponents to form a biofuel composition, is not fractionated after anFCC process. Moreover, after an FCC process, the final cracked product,with or without blending to one or more additional components to form abiofuel composition, is not further separated and/or distilled (e.g.,for additional purification processes) from all the reaction mixture(s)formed during the cracking process, with the exception of optionallyremoving water. The final cracked product, with or without blending toone or more additional components to form a biofuel composition, may bestored, manufactured, commercialized and/or employed as is, after an FCCprocess. Alternatively, the final cracked product can be blended withone or more additional components to form a biofuel composition.

In at least one embodiment, a refinery method and system may include anassembly for introducing the HTL oil, such as an HTL-processed oil, inan amount of at least about 1 wt % of the HTL oil, such as about 1 wt %to about 20 wt % of the HTL oil, into an FCC unit or field upgraderoperation with the contact time of the cracking catalyst being for aperiod of about 0.5 seconds to about 40 minutes, such as from about 1second to about 30 minutes, such as from about 30 seconds to about 15minutes, such as from about 1 minute to about 5 minutes, alternatelyfrom about 5 minutes to about 40 minutes.

Furthermore, the HTL oil can be conditioned prior to introduction intothe refinery process (e.g., FCC reactor unit) and can be made fromseveral compositions as discussed above.

In at least one embodiment, an HTL oil is produced from the HTLconversion of biomass under the conditions of 200° C. to 425° C. (e.g.,350° C.), at a processing residence time of at least 1 minute, such asfrom 1 minutes to 2h, such as from 5 minutes to 30 minutes, either withor without a catalyst. An example of a catalyst used for the crackingprocess may be Y-Zeolite, ZSM-5 or other FCC catalyst, or mixturesthereof (further details will be provided below). A catalyst additivecan be added to optimize the performance of the FCC catalyst whenprocessing HTL oil.

In at least one embodiment, a hydrocarbon co-feed, for example derivedfrom upgrading petroleum, includes a gas oil (GO) feedstock, a vacuumgas oil (VGO) feedstock, a heavy gas oil (HGO) feedstock, LPG, a middledistillate feedstock, a heavy-middle distillate feedstock, ahydrocarbon-based feedstock, Resid/De-Asphalted Oil (DAO) orcombinations thereof. The hydrocarbon co-feed may be gasoline or diesel.Where a catalyst is used, the catalyst/oil ratio can be in the range ofabout 2/1 to 10/1, such as about 3/1 to 9/1, 4/1 to 8/1, or 5/1 to 7/1,where oil in this ratio is the total amount of oil feedstock introduced(e.g., hydrocarbon co-feed and the HTL oil feedstock).

In at least one embodiment, the amount of the HTL oil feedstock that maybe introduced into a refinery for co-processing with a hydrocarbonco-feed, is in the range of from about 1 wt % to about 20 wt %, such asfrom about 2 wt % to about 15 wt %, such as from about 3% to about 10%,such as from about 4% to about 8%, relative to the total amount offeedstock introduced into the refinery for processing (e.g., hydrocarbonco-feed and the HTL oil feedstock). For example, the amount of HTL oilfeedstock introduced into the cracking conversion unit for co-processingwith a hydrocarbon co-feed, may be 1 wt %, relative to the total amountof feedstock introduced into the refinery for processing, such as 2 wt%, such as 3 wt %, such as 4 wt %, such as 5 wt %, such as 6 wt %, suchas 7 wt %, such as 8 wt %, such as 9 wt %, such as 10 wt %, such as 11wt %, such as 12 wt %, such as 13 wt %, such as 14 wt %, such as 15 wt%, such as 16 wt %, such as 17 wt %, such as 18 wt %, such as 19 wt %,such as 20 wt %, relative to the total amount of feedstock introducedinto the refinery for processing.

Injection System coupled to the Cracking unit

In at least one embodiment, an HTL oil is fed to a cracking reactor in aliquid state and/or in a gaseous state, or in a partiallyliquid-partially gaseous state. When injected into the reactor in aliquid state, and/or in a gaseous state, or in a partiallyliquid-partially gaseous state, the HTL oil can be vaporized upon entry,such that the HTL oil can be contacted in the gaseous state with thecracking catalyst.

Furthermore, a catalytic cracking process may include contacting the HTLoil and a fluid hydrocarbon co-feed (e.g., petroleum oil) with acracking catalyst, such as in an FCC reactor with an FCC catalyst, at atemperature of about 400° C. to about 700° C., such as about 545° C. toabout 585° C., to produce one or more cracked products.

In at least one embodiment, the fluid hydrocarbon co-feed is anynon-solid hydrocarbon co-feed suitable as a co-feed for a catalyticcracking unit. For example, the fluid hydrocarbon co-feed can beobtained from a conventional crude oil (also sometimes referred to as apetroleum oil or mineral oil), an unconventional crude oil (that is, oilproduced or extracted using techniques other than the traditional oilwell method) or a Fisher Tropsch oil, and/or any hydrocarbon listedabove, and/or a mixture thereof.

In at least one embodiment, the fluid hydrocarbon co-feed is a fluidhydrocarbon co-feed from a renewable source, such as a vegetable oil.

Furthermore, the fluid hydrocarbon co-feed may include a fraction of arenewable oil and/or crude oil, such as straight run (atmospheric) gasoils, flashed distillate, vacuum gas oils (VGO), light cycle oil, heavycycle oil, hydrowax, coker gas oils, diesel, gasoline, kerosene,naphtha, liquefied petroleum gases, atmospheric residue (“long residue”)and vacuum residue (“short residue”) and/or mixtures thereof. The fluidhydrocarbon co-feed may include paraffins, olefins and aromatics, and/ormixtures thereof.

In a at least one embodiment, the fluid hydrocarbon co-feed includes atleast about 5 wt % elemental hydrogen (i.e., hydrogen atoms) or greater,such as about 10 wt % elemental hydrogen or greater, such as from about5 wt % to about 20 wt % elemental hydrogen based on the total fluidhydrocarbon co-feed on a wet biomass basis. A high content of elementalhydrogen, such as a content of at least 5 wt %, allows the hydrocarbonfeed to act as an inexpensive hydrogen donor in the catalytic crackingprocess.

In at least one embodiment, a fluid hydrocarbon co-feed is present at aweight ratio of fluid hydrocarbon co-feed to the HTL oil of 4:6, such as4.5:5.5, such as 5:5, such as 5.5:4.5, such as 6:4, such as 6.5:3.5:,such as 7:3, such as 7.5:2.5, such as 8:2, such as 8.5:1.5, such as 9:1,such as 9.5:0.5, such as 9.8:0.2, such as 9.9:0.1. The fluid hydrocarbonco-feed and the HTL oil can be fed to an FCC reactor in a weight ratiowithin the above ranges.

The amount of the HTL oil, based on the total weight of the HTL oil andfluid hydrocarbon co-feed supplied to an FCC reactor, can be from about65 wt % to about 0.05 wt %, such as from about 60 wt % to about 0.1 wt%, such as from about 55 wt % to about 1 wt %, such as from about 50 wt% to about 2.5 wt %, such as from about 45 wt % to about 5 wt %, such asfrom about 10 wt % to about 40 wt %.

The catalytic cracking process can be carried out in an FCC reactor. AnFCC reactor is part of an FCC unit. Suitable FCC reactors can be, forexample, a fixed bed reactor, a circulating fluidized bed reactor, afluid bed reactor (such as a fluidized dense bed reactor), a moving bedreactor, an FCC riser reactor, a multiple FCC riser reactor, and/or ahybrid reactor such as one or more of these cited reactors can becoupled together, and the like. In at least one embodiment, thecatalytic cracking process is carried out in an FCC riser reactor, suchas the FCC reactor is the FCC riser reactor. The fluid hydrocarbonco-feed can be supplied to such FCC riser reactor downstream of thelocation where one or more liquefied product(s) can be supplied to theFCC riser reactor.

In at least one embodiment, a mixture of one or more liquefiedproduct(s) with a first hydrocarbon co-feed is supplied to a crackingreactor, such as an FCC riser reactor, at a first location and a secondfluid hydrocarbon co-feed is supplied to the cracking reactor, such asthe FCC riser reactor, at a second location downstream of the firstlocation. The HTL oil and the hydrocarbon co-feed are injected into thecracking reactor through separate injection nozzles.

In at least one embodiment, a mixture of one or more HTL oil(s) and afirst hydrocarbon co-feed, such as an organic solvent when the organicsolvent is chosen from the described fluid hydrocarbon co-feeds, issupplied to an FCC reactor, such as an FCC riser reactor, at a firstlocation and a second fluid hydrocarbon co-feed is supplied to the FCCreactor, such as the FCC riser reactor, at a second location downstreamof the first location.

Suitable conventional reactor types are described in for example U.S.Pat. Nos. 4,076,796; 6,287,522 (dual riser); Fluidization Engineering,D. Kunii and O. Levenspiel, Robert E. Krieger Publishing Company, NewYork, N.Y. 1977; Fluid Catalytic Cracking technology and operations,Joseph W. Wilson, PennWell Publishing Company, 1997, chapter 3, pages101 to 112; Riser Reactor, Fluidization and Fluid-Particle Systems,pages 48 to 59, F. A. Zenz and D. F. Othmo, Reinhold PublishingCorporation, New York, 1960; U.S. Pat. No. 6,166,282 (fast-fluidized bedreactor); U.S. patent application Ser. No. 09/564,613 filed May 4, 2000(multiple riser reactor), the disclosures of which are incorporatedherein by reference.

For purposes of the present disclosure, the FCC riser reactor can be anelongated tube-shaped reactor suitable for carrying out any catalyticcracking reactions. The elongated tube-shaped FCC riser reactor can beoriented in a vertical manner.

The FCC riser reactor may be an “internal” FCC riser reactor or an“external” FCC riser reactor, such as the FCC riser reactor is aninternal FCC riser reactor that is a vertical tube-shaped reactor, whichmay have a vertical upstream end located outside a vessel and a verticaldownstream end located inside the vessel. The vessel can be a reactionvessel suitable for catalytic cracking reactions and/or a vessel thatmay include one or more cyclone separators and/or swirl tubes toseparate catalyst from cracked product. Usage of an internal riserreactor may advantageously prevent from any potential clogging and/orfouling that may occur during the FCC process.

The length of the riser reactor may vary widely. For purposes of thepresent disclosure, the FCC riser reactor may have a length in the rangeof from about 1 meter (3.28 feet) to about 100 meters (328 feet), suchas from about 5 meters (16.4 feet) to about 75 meters (246 feet), suchas from about 10 meters (32.8 feet) to about 60 meters (196.8 feet),such as from about 15 meters (49.2 feet) to about 50 meters (164 feet).

In at least one embodiment, the HTL oil produced in the HTL process issupplied to an FCC riser reactor, at the bottom of the FCC riserreactor. This may advantageously result in an in-situ water formation atthe bottom of the reactor. The in-situ water formation may lower thehydrocarbon partial pressure and reduce second order hydrogen transferreactions, thereby resulting in higher olefin yields. In at least oneembodiment, the hydrocarbon partial pressure is lowered to a pressure inthe range of from about 0.01 to 0.50 MPa, such as from 0.05 to 0.45 MPa,such as from 0.1 to 0.40 MPa, such as from 0.15 to 0.35 MPa, such asfrom 0.10 to 0.30 MPa.

A number of riser designs use a lift gas as a further means of providinga uniform catalyst flow. Lift gas is used to accelerate the catalyst ina first section of the riser before introduction of the feed and therebyreduces the turbulence which can vary the contact time between thecatalyst and hydrocarbons. Hence, there is better catalyst/oilcontacting when a lift gas is used, and, without being bond by theory,it is believed that the lift gas can “condition” the FCC catalyst, sothat its performance increases in the cracking reactor. Therefore,adding a lift gas at the bottom of the FCC riser reactor could bebeneficial for the process.

Suitable lift gas may include, but are not limited to, steam, vaporizedoil and/or oil fractions, and/or mixtures thereof. However, the use of avaporized oil and/or oil fraction (such as vaporized liquefied petroleumgas, gasoline, diesel, kerosene or naphtha) as a lift gas may have theadvantage that the lift gas can simultaneously act as a hydrogen donorand may prevent or reduce coke formation. Further, if a fluidhydrocarbon co-feed is used as an organic solvent in the FCC process,also vaporized organic solvent may be used as a lift gas. Alternatively,a heavy feed such as a gas oil, a VGO, may be added to the FCC riserreactor via feed injection nozzles. The catalyst is pre-accelerated upthe FCC riser upstream of the feed by injection of lift gas to the baseof the riser.

One or more HTL oil(s) and/or any fluid hydrocarbon feed may flowco-currently in the same direction. The FCC catalyst can be contacted ina concurrent-flow, countercurrent-flow or cross-flow configuration withsuch a flow of the HTL oil(s) and optionally the fluid hydrocarbon feed.In at least one embodiment, the FCC is contacted in a concurrent-flowconfiguration with a concurrent-flow of the HTL oil(s) and optionallythe fluid hydrocarbon feed.

Potential contaminants present in a hydrocarbons feedstock fed to an FCCreactor, can be vanadium, nickel, sodium, and iron. The catalyst used inthe FCC unit may favor the absorption of these contaminants which maythen have unfavorable effects on the hydrocarbons conversion into abiofuel in the FCC reactor. The main advantage of co-feeding an HTL oilwith one or more hydrocarbon(s) to an FCC reactor can be that therenewable oil contains little or none of these contaminants, thusbeneficially extending the life of the catalyst, and enabling tomaintain greater catalyst activity while improving the magnitude of theconversion into biofuel(s).

In at least one embodiment, a system (also referred to as an apparatus)used for processing or co-processing a hydrocarbons feedstock, an HTLoil, or combinations thereof, includes a refinery system, such as aconversion unit, such as an FCC unit, a coker, a coking unit, a fieldupgrader unit, a hydrotreater, a hydrotreatment unit, a hydrocracker, ahydrocracking unit, and/or a desulfurization unit. For instance, thesystem used for the hydrocarbons conversion into a biofuel may be orinclude an FCC unit operation; may be or include a coker; may be orinclude a hydrotreater; may be or include a hydrocracker. A conversionsystem of hydrocarbons into biofuel used for processing or co-processinga hydrocarbon co-feed, an HTL oil, or combinations thereof, may includea retrofitted refinery system, such as a refinery system including aretrofitted port for the introduction of an HTL oil. For example, theconversion system of hydrocarbons into biofuel used for processing orco-processing a hydrocarbon co-feed, an HTL oil, or combinationsthereof, may include a retrofitted FCC refinery system having at leasttwo or more retrofitted port(s) for introducing an HTL oil. For example,a retrofitted port may be a stainless steel port, a titanium or someother alloy or a combination thereof of high durability, high corrosiveenvironment material.

In at least one embodiment, a refinery system used for processing ahydrocarbon co-feed with an HTL oil includes a retrofitted refinerysystem, a FCC, a retrofitted FCC, a coker, a retrofitted coker, a fieldupgrader unit, a hydrotreater, a retrofitted hydrotreater, ahydrocracker, or a retrofitted hydrocracker.

In at least one embodiment, the process of the present disclosure forconverting hydrocarbons into biofuel(s) includes introducing, injecting,feeding, co-feeding, an HTL oil into a refinery system via a mixingzone, at least two or more nozzles, at least two or more retrofittedports, at least two or more retrofitted nozzles, one or more velocitysteam line, or a live-tap. For example, the process of the presentdisclosure for converting hydrocarbons into biofuel(s) may includeprocessing a hydrocarbon co-feed with an HTL oil. In at least oneembodiment, the process may include co-injecting a hydrocarbon co-feedand an HTL oil, such as co-feeding, independently or separatelyintroducing, injecting, feeding, or co-feeding, a hydrocarbon co-feedand an HTL oil into a refinery system. For example, a hydrocarbonco-feed and an HTL oil may be provided, introduced, injected, fed, orco-fed at a close distance from each other into the FCC reactor, thereaction zone, the FCC reaction riser of the refinery system.Furthermore, the HTL oil may be introduced, injected, fed, co-fed intothe FCC reactor, the reaction zone, or the FCC reaction riser of therefinery system near, upstream, and/or downstream to the delivery orinjection point of the hydrocarbon co-feed. The hydrocarbon co-feed andthe HTL oil can be contacted with each other upon introduction,delivery, injection, feeding, co-feeding into the refinery system, intothe reactor, into the reaction zone, or into the FCC reaction riser. Inat least one embodiment, the hydrocarbon co-feed and the HTL oil arecontacted with each other subsequent to entering the refinery system,the reactor, the reaction zone, or the FCC reaction riser. Thehydrocarbon co-feed and the HTL oil may be first contacted with eachother subsequent to entering into, introduction into, injection into,feeding into, or co-feeding into the refinery system, the reactor, thereaction zone, or the FCC reaction riser. In at least one embodiment,the hydrocarbon co-feed and the HTL oil are co-blended prior toinjection into the refinery system.

The hydrocarbon co-feed and the HTL oil may be introduced, injected,fed, co-fed into the refinery system through different or similardelivery systems. For example, the hydrocarbon co-feed and the HTL oilmay be introduced into the refinery system through at least two or moreindependent or separate injection nozzles. The hydrocarbon co-feed andthe HTL oil may be introduced into the refinery system near to eachother in a FCC reactor riser in the refinery system. The HTL oil may beintroduced, injected, fed, co-fed into the refinery system above, below,near the introduction point of the hydrocarbon fuel feedstock in therefinery system. In at least one embodiment, at least two or moreinjection nozzles are located in a FCC reactor riser in the refinerysystem suitable for introducing the hydrocarbon fuel feedstock and/orthe HTL oil. The HTL oil may be introduced into the refinery systemthrough a lift steam line located at the bottom of the FCC reactorriser. The hydrocarbon co-feed may be introduced into the refinerysystem at a first injection point and the renewable fuel oil may beintroduced into the refinery system at a second injection point. Thefirst injection point can be, for example, upstream of the secondinjection point, alternatively, and/or downstream of the secondinjection point, and/or near to the second injection point, and/or thefirst injection point and the second injection point may be located in areactor riser, such as an FCC reactor riser. In at least one embodiment,an HTL oil may be introduced below an FCC reactor riser during theconversion process of the hydrocarbon co-feed. Additionally, an HTL oilmay be injected via a quench riser system upstream, downstream, or near,from the introduction point of the hydrocarbon co-feed. In at least oneembodiment, an HTL oil is injected via a quench riser system locatedabove, below, or near, a petroleum fraction feedstock injection nozzle.

In at least one embodiment, the processing of the hydrocarbon co-feedwith the HTL oil has a substantially equivalent or greater performancein preparing the biofuel product, relative to processing solely thehydrocarbon co-feed in the absence of the HTL oil. In at least oneembodiment, processing an amount of up to 30 wt %, such as up to 20 wt%, of HTL oil with the remainder hydrocarbon co-feed, for instance0.05:99.95, such as 1:99, such as 2:98, such as 3:97, such as 4:96, suchas 5:95, such as 10:90, such as 20:80 weight ratio of HTL oil to thehydrocarbon co-feed may have a substantially equivalent or greaterperformance in the resulting fuel products, relative to processingsolely the hydrocarbon co-feed in the absence of the HTL oil. In atleast one embodiment, processing in the range of from 20:80 to0.05:99.95 weight ratio of an HTL oil with a hydrocarbon co-feed resultsin a weight percent increase in gasoline or diesel of more than 0.05 wt%, such as 0.5 wt % or greater, such as 1 wt % or greater, such as 1.5wt % or greater, such as 2 wt % or greater, such as 5 wt % or greater,such as 10 wt % or greater, such as 20 wt % or greater, relative toprocessing solely the hydrocarbon co-feed in the absence of the HTL oil.

In at least one embodiment, a suitable amount of one or more HTL oil(s)(such as from 2 wt % to 20 wt % relative to the total weight offeedstock fed) of one or more HTL oil(s), is blended with one or morevariety of hydrocarbon oils and/or blends of hydrocarbon oils includingHGO (Heavy Gas Oil), LGO (Light Gas Oil), VGO (Vacuum Gas Oil), andother petroleum fractions and blends.

For example, an HGO may be a lighter feedstock that can be combined withone or more hydrocarbon oil(s), as in a mixed feed stream or as aseparate feed stream, either before, or after, alternatively before andafter, the introduction of one or more hydrocarbon oil(s). In at leastone embodiment, an HGO is directed to a refinery FCC unit. In analternate embodiment, a hydrocarbon oil is introduced jointly with anHTL oil, before, or after, alternatively before and after theintroduction of the HTL oil. Either the HTL oil or the hydrocarbon oil,or both, may be alternatively fed in a pulse manner. In at least oneembodiment, a hydrocarbon oil is introduced jointly with an HTL oil(e.g., a cellulosic RIN-compliant fuel) in the feed of a refinery FCCunit.

A suitable amount of an HTL oil, such as a cellulosic RIN-compliantfuel, may be blended with a VGO. VGO can be a feedstock fed to arefinery FCC unit. In at least one embodiment, a blend of HTL oil, suchas a cellulosic RIN-compliant fuel, and VGO targets a final measured TAN(also referred to as “Total Acid Number”) of the cracked product(s) ofless than 4, such as less than 2, such as less than 1, such as in arange of from 0.05 to 1, such as from 0.05 to 0.5, such as from 0.05 to0.25.

In at least one embodiment, a suitable amount of HTL oil is blended(e.g., by co-feeding) with an HGO (e.g., a lighter feedstock) that canbe directed to a refinery FCC unit, thus either in combination with aVGO or as a separate feed.

In at least one embodiment, a suitable amount of HTL oil is blended(e.g., by co-feeding) with lighter hydrocarbon co-feeds such as a lightcycle oil (LCO), or gasoline, or diesel, with or without a surfactant,alternatively with or without any additive(s). The content of LCO,and/or gasoline, and/or diesel blended with an HTL oil may be of about0.005 wt % to about 98 wt %, such as from about 0.005 wt % to about 90wt %, such as from about 0.005 wt % to about 80 wt %, such as from about0.005 wt % to about 70 wt %, such as from about 0.005 wt % to about 60wt %, such as from about 0.005 wt % to about 50 wt %, such as from about0.005 wt % to about 40 wt %.

Suitable HTL oil may include all of the whole fuel produced from thethermal or catalytic conversion of biomass, such as a whole fuelproduced from the thermal or catalytic conversion of biomass with a lowwater content (e.g., at least less than 15%).

In at least one embodiment, the flash point of an HTL oil is increasedin order to reduce the volatile content of the liquid and subsequentlyco-processed in an FCC with a hydrocarbon feedstock. The flash point maybe increased, for example, from 50° C. to 70° C., or greater and can bemeasured by the Pensky-Martens closed cup flash point tester (e.g. ASTMD-93). However, various methods and apparatus can be used to effectivelyreduce the volatile components, such as flash column, falling filmevaporator, devolatilization vessel or tank. If present, reduction ofsome of the volatile components of the HTL oil may improve the reductionof undesirable components such as phenols from passing through the FCCreactor and ending up in the collected water stream.

Not only do biofuel feedstocks like corn, switchgrass, and agriculturalresidues need water for growth and conversion to bioethanol, butpetroleum feedstocks like crude oil and oil sands also require largevolumes of water for drilling, extraction and conversion into petroleumproducts. Hence, the initial HTL process of the HTL oil beforeintroduction to the FCC unit is advantageous since only less than about12% of water and less than about 5% of oxygenates are present,preventing undesirable components to interfere with the HTL oil, thehydrocarbon, and the catalyst during the conversion process to biofuel.For example, the water content of an HTL oil feedstock that may beintroduced into a refinery FCC unit for co-processing with a hydrocarbonco-feed (e.g., VGO), may be less than about 12%, such as in the range ofabout 0.01 wt % to about 12 wt %, such as from about 1 wt % to about 10wt %, such as from about 1.5 wt % to 5 wt %. In at least one embodiment,the water content of the HTL oil feedstock introduced into the refineryFCC unit for co-processing with a hydrocarbon co-feed (e.g., VGO) isless than about 12%, such as in the range of about 0.01 wt % to about 12wt %, such as from about 1 wt % to about 10 wt %, such as from about 1.5wt % to 5 wt %.

For purposes of the present disclosure, a hydrocarbon co-feed can be orinclude an organic solvent which may include a polar and/or a non-polarhydrocarbon compounds (e.g., LCO). In at least one embodiment, theorganic solvent includes at least one or more polar hydrocarboncompounds, such as the organic solvent includes more than one, such asmore than two, such as more than three different polar hydrocarboncompounds.

In at least one embodiment, the organic solvent includes one or morecarboxylic acids. A carboxylic acid refers to a hydrocarbon compoundincluding at least one carboxyl (—COOH) group, such as the carboxylicacids can be polar hydrocarbon compounds. The organic solvent includesequal to or more than about 1 wt % carboxylic acids, such as equal to ormore than about 3 wt % carboxylic acids, such as equal to or more thanabout 5 wt % of carboxylic acids, such as equal to or more than about 10wt % of carboxylic acids, such as equal to or more than about 15 wt % ofcarboxylic acids, such as equal to or more than about 20 wt % ofcarboxylic acids, such as equal to or more than about 25 wt % ofcarboxylic acids, such as equal to or more than about 30 wt % ofcarboxylic acids, such as equal to or less than about 95 wt % ofcarboxylic acids, such as equal to or less than about 90 wt % ofcarboxylic acids, such as equal to or less than about 85 wt % ofcarboxylic acids, such as equal to or less than about 80 wt % ofcarboxylic acids, such as equal to or less than about 70 wt % ofcarboxylic acids, based on the total weight of organic solvent.

Suitable organic solvents, including one or more carboxylic acids, canbe, but are not limited to, formic acid, acetic acid, propionic acid,butyric acid, 4-oxopentanoic acid acid (also called “levulinic acid”),pentanoic acid (also called “valeric acid”), caproic acid, and/orbenzoic acid. In at least one embodiment, the carboxylic acid solventincluded in the organic solvent is acetic acid. Acetic acid can besimultaneously used as part of the organic solvent and/or used as anacid catalyst.

In an alternate embodiment, an organic solvent includes paraffiniccompounds, naphthenic compounds, olefinic compounds and/or aromaticcompounds. Such compounds may be present in refinery streams such as gasoil, fuel oil and/or residue oil. These refinery streams may thereforealso be suitable as organic solvent in the cracking process.

In at least one embodiment, a hydrocarbon co-feed includes at least aportion of cracked product(s), such as a portion of the crackedproduct(s) may be recycled to the cracking process and further used asorganic solvent. In at least one embodiment, equal to or more than about5 wt %, such as equal to or more than about 10 wt %, such as equal to ormore than about 15 wt %, such as equal to or more than about 20 wt %,such as equal to or more than about 25 wt %, such as equal to or morethan about 30 wt % of the organic solvent is obtained from anintermediate and/or a final cracked product.

In at least one embodiment, any recycle of cracked product(s) includes aweight amount of cracked product(s) of 1 to 150 times the weight of theHTL oil, such as 2 to 100 times the weight of the HTL oil, such as 5 to50 times the weight of the HTL oil, such as 10 to 20 times the weight ofthe HTL oil.

In at least one embodiment, at least part of the hydrocarbon co-feed isderived from a cellulosic material, such as a lignocellulosic materialand/or a hemicellulosic material, such as a lignocellulosic material.For example, at least part of the hydrocarbon co-feed may be generatedin-situ during liquefaction of the cellulosic material, such as alignocellulosic material and/or a hemicellulosic material, such as alignocellulosic material. In another example, at least part of thehydrocarbon co-feed may be obtained by acid hydrolysis of a cellulosicmaterial, such as a lignocellulosic material and/or a hemicellulosicmaterial, such as a lignocellulosic material, such as a lignocellulosicmaterial. Examples of possible hydrocarbon compounds in the hydrocarbonco-feed that may be obtained by acid hydrolysis of a cellulosicmaterial, such as a lignocellulosic material and/or a hemicellulosicmaterial, such as a lignocellulosic material, may include formic acid,acetic acid, and levulinic acid.

Further, suitable hydrocarbon compounds attainable from such acidhydrolysis products by hydrogenation may also be used. Examples of suchhydrogenated hydrocarbon compounds may include, but are not limited to,tetrahydrofufuryl compounds (derived from furfural via hydrogenation),tetrahydropyranyl compounds (derived from hydroxymethylfurfural),gamma-valerolactone (derived from levulinic acid via hydrogenation),ketones, mono- and di-alcohols (derived from sugars) and guaiacol andsyringol compounds (derived from lignin). In at least one embodiment,the hydrocarbon co-feed includes one or more of such hydrocarboncompounds. Such hydrocarbon compounds may also be included in the finalcracked product. Accordingly, in at least one embodiment, the finalcracked product or part thereof includes one or more of the hydrocarboncompounds listed, optionally hydrogenated, compounds such as guaiacoland/or syringol compounds, which can be derived from lignin.

One or more hydrocarbon compounds in the hydrocarbon co-feed mayadvantageously be obtainable from the HTL oil cracked in the crackingprocess. The hydrocarbon compound(s) may for example be generatedin-situ and/or recycled and/or used as a make-up hydrocarbon co-feed,affording significant economic and processing advantages.

During FCC, in at least one embodiment, the hydrocarbon co-feed includesone or more hydrocarbon compounds that may be suitable to act as a fluidhydrocarbon co-feed in the catalytic cracking phase. The hydrocarbonco-feed used during cracking may include, one or more hydrocarboncompounds obtained from, for example, a crude oil (e.g., a petroleum oilor mineral oil), a renewable source (e.g., HTL oil), and/or a mixturethereof, such as the hydrocarbon co-feed used during cracking mayinclude a fraction of a petroleum oil or renewable oil. Suitablehydrocarbon co-feed may include, but are not limited to, diesel,gasoline, kerosene, naphtha, liquefied petroleum gases, VGO, a straightrun (atmospheric) gas oils, atmospheric residue (“long residue”) andvacuum residue (“short residue”), flashed distillate, light cycle oil,heavy cycle oil, hydrowax, coker gas oils, and/or mixtures thereof. Inat least one embodiment, hydrocarbon co-feed include(s) diesel,gasoline, VGO and/or mixtures thereof.

A co-solvent may be used in addition to the hydrocarbon co-feed alreadyavailable in the FCC in order 1) to enhance the solvent power; and 2) toincrease the solubility of poorly-soluble components present during thecracking process. Suitable co-solvent can be an organic solvent thatincludes hydrocarbons, such as a petroleum oil or a fraction thereof.Such hydrocarbon co-feed or organic co-solvent may be a suitable feed tothe catalytic cracking phase. Furthermore, no separation of thehydrocarbon co-feed or organic co-solvent may be required.

Optionally, one or more cracked product(s) can be subsequentlyhydrotreated with a source of hydrogen, such as in the presence of ahydrotreatment catalyst to produce a hydrotreated cracked product. Forinstance, a hydrotreatment process may include hydrodeoxygenation,hydrodenitrogenation and/or hydrodesulphurization. One or morehydrotreated product(s) derived therefrom can conveniently be used as abiofuel composition. Such biofuel composition may conveniently beblended with one or more other components (e.g., additives) to produce abiofuel composition. Examples of such components may include, but arenot limited to, anti-oxidants, corrosion inhibitors, ashless detergents,dehazers, dyes, lubricity improvers and/or mineral fuel components,conventional petroleum derived gasoline, diesel and/or kerosenefractions.

In at least one embodiment, the FCC process includes contacting an HTLoil (e.g., a cellulosic material) concurrently with the fraction of ahydrocarbon (e.g., petroleum oil), with a source of hydrogen, with ahydrogenation catalyst, and optionally with an acid catalyst, at atemperature of equal to or more than about 100° C. to produce a crackedproduct (e.g., final (RINs)biofuel product(s)). In the FCC unit,cracking and hydrogenation of the HTL oil and hydrocarbons may becarried out simultaneously or hydrogenation may be carried outsubsequent to the cracking.

In at least one embodiment, a mixture of one or more liquefiedproduct(s) with a first hydrocarbon co-feed is supplied to an FCCreactor, such as an FCC riser reactor, at a first location and a secondfluid hydrocarbon co-feed is supplied to the FCC reactor, such as theFCC riser reactor, at a second location downstream of the firstlocation. In at least one embodiment, a mixture of one or more HTLoil(s) and a first hydrocarbon co-feed, such as an organic solvent whenthe organic solvent is chosen from the described fluid hydrocarbonco-feeds, is supplied to an FCC reactor, such as an FCC riser reactor,at a first location and a second fluid hydrocarbon co-feed is suppliedto the FCC reactor, such as the FCC riser reactor, at a second locationdownstream of the first location.

In at least one embodiment, the FCC unit is designed to have at leasttwo feedstock injection points, such as two or more feedstock injectionpoints, such as at least one injection point for a petroleum oil co-feedand at least one injection point for an HTL oil feedstock. For example,an FCC unit has at least two injection points for co-injection of amixture of a petroleum fraction feedstock and an HTL oil feedstock (bothpetroleum fraction feedstock and HTL oil feedstock can be mixed upstreamof the injection point) or the system could be fitted with multiplepoints of injection for either, both or mixtures of the feedstock. In analternate embodiment, the FCC unit is retrofitted to include a way ofintroducing the HTL oil, for example, by adding an injection point closeto the FCC riser or at some point in the process where the catalyst maybe upflowing. A suitable FCC unit fitted with at least two feedstockinjection points is described in U.S. Pat. No. 9,129,989 which isincorporated herein by reference.

Processes of the present disclosure can provide biofuel compositions(e.g., biolfuel compositions having RIN credits) without any separationprocess of the cracked product(s) after FCC providing additional time-,energy- and cost-efficiency. Furthermore, an FCC unit fitted with two ormore feedstock injection points where the FCC unit is located downstreamfrom a hydrothermal liquefaction unit provides biofuel compositions witha total acid number (TAN) of about 3 mg or greater KOH/g, such as about6 mg or greater KOH/g, The FCC process can be performed using a systemof at least two or more injection nozzles on the FCC unit, whichpromotes better blending of the HTL and hydrocarbon oils (and ultimatelycracked product(s)) by increasing the gas/oil dispersion, providingadditional time-, energy- and cost-efficiency.

In at least one embodiment, processed and/or unprocessed HTL oil is fedupstream and/or downstream of a hydrocarbon (e.g., gas oil (GO); VGO)feed inlet. The HTL oil can be introduced in an upstream and/or adownstream section of the FCC riser onto the FCC catalyst, thus enablingthe hydrocarbons conversion into a biofuel, such as the HTL oil can beintroduced downstream of the FCC riser. Introduction of the HTL oil inupstream and/or downstream section of the FCC riser may therebyimparting properties of the renewable oil (e.g., viscosity of the oil;acid nature; oxidation stability; etc.) In an alternate embodiment, anHTL oil is introduced downstream of the hydrocarbons fresh feedinjection nozzles. Optionally, a retrofitted riser with a retrofittedrenewable oil feedstock injection port(s) can be added to the presentsystem. The term “retrofitting” refers to the addition of new technologyor features to older systems, such as to install new or modified partsor equipment in something previously manufactured or constructed. TheFCC riser may be adapted to include multiple renewable oil feedstockinjection port(s) both before and after the introduction of thehydrocarbons. Furthermore, The FCC riser may be retrofitted to have onlyone additional renewable oil feedstock injection port positioned eitherbefore or after the hydrocarbons injection point, alternativelyretrofitted to have one or more renewable oil feedstock injection(s)port along the hydrocarbons feedstock feed line.

The FCC unit may include a riser quench system which may injectvaporizable quench oil into the FCC riser above the hydrocarbons feedinjection nozzles. Introduction of a quench oil, such as vegetable oil,may increase the temperature in the mix zone and lower section of theFCC riser. In at least one embodiment, the HTL oil feedstock may beinjected into the quench line of the FCC riser.

In at least one embodiment, the FCC process includes contacting an HTLoil with an organic solvent, optionally in the presence of an acidcatalyst, at a temperature of at least about 90° C., such as from about90° C. to about 700° C., such as from about 400° C. to about 700° C.,such as from about 545° C. to about 585° C.

In at least one embodiment, the catalyst is an acid catalyst suitablefor cracking of the HTL oil and/or hydrocarbon co-feed, sufficientlystrong to enable cleavage of the covalent linkages and dehydration ofthe HTL oil and hydrocarbons. Suitable acid catalysts can be, but arenot limited to, a Bronsted acid or a Lewis acid. The acid catalyst ofthe process of the present disclosure may be a homogeneous catalyst or aheterogeneous catalyst, such as the acid catalyst can be a homogeneousor a finely dispersed heterogeneous catalyst, such as the acid catalystis a homogeneous catalyst. Furthermore, the acid catalyst can bemaintained as a stable liquid under the cracking conditions used duringthe process.

The acid catalyst can be a Bronsted acid, such as a mineral or anorganic acid, such as a mineral or an organic acid having a pKa value offrom about 2 to 6, such as from about 2.2 and 4, such as from 2.5 and 3.Suitable mineral acids may include, but are not limited to, hydrochloricacid (HCl), nitric acid (HNO₃), sulphuric acid (H₂SO₄), Boric acid(H₃BO₃), para-toluene sulphonic acid, phosphoric acid (H₃PO₄),Hydrobromic acid (HBr), and mixtures thereof In at least one embodiment,the acid catalyst used in the cracking process is sulphuric acid orphosphoric acid. Suitable organic acids for the FCC process may include,but are not limited to, formic acid, acetic acid, oxalic acid, lacticacid, levulinic acid, citric acid, trichloracetic acid and mixturesthereof.

The acid catalyst can be present in an amount of from about 0.005 wt %to about 50 wt %, such as from about 0.01 wt % to about 45 wt %, such asfrom about 0.05 wt % to about 40 wt %, such as from about 0.1 wt % toabout 35 wt %, such as from about 0.5 wt % to about 30 wt %, such asfrom about 0.75 wt % to about 25 wt %, such as from about 1 wt % toabout 20 wt %, such as from about 2 wt % to about 15 wt %, such as fromabout 5 wt % to about 15 wt %, based on the total weight of the organicsolvent and/or solvent mixture, and the acid catalyst.

Strongly acidic catalyst sites on the catalyst promote cracking. Hence,the hydrogen forms of zeolites used in FCC unit systems are powerfulsolid-based acids, promoting various acid-catalyzed based reactions(e.g., cracking, isomerisation, alkylation, dehydration of alcohols,hydrogenation of the polyaromatics). The hydrogen forms of zeolites caneffectively promote hydrogen transfer, thus with longer reactorresidence times. The present FCC unit system benefits from thecharacteristics of renewable oil, namely its TAN or acidic nature, thatcan lead to an improvement in cracking or the conversion of, forexample, VGO (i.e., a synergistic effect) in FCC operations.Consequently, such procedure advantageously promotes the production ofdesirable products by reducing unwanted products by way of heavy cycleoil and clarified slurry oil. Further, additives, such assulfur-reducing additives, may be added to the catalyst. It isanticipated that such additives may experience enhanced effectiveness.

The FCC catalyst can be any suitable catalyst for use in a crackingprocess. In at least on embodiment, the FCC catalyst includes anysuitable zeolitic component for the FCC. Also, the FCC catalyst maycontain an amorphous binder compound and/or a filler. Examples of theamorphous binder component may include quartz, zirconia, silica,alumina, magnesium oxide, calcium carbonate, and/or titania, and/or amixture thereof of at least two or more of these components. Suitablefillers may include clays (such as hydrated aluminum silicate, alsocalled “kaolin”) and/or silica. For purpose of the present disclosure,the zeolitic component can be a large, a medium, and/or a mixturethereof of large and medium pore zeolite which may include a porous,crystalline aluminosilicate structure.

In at least one embodiment, a porous, crystalline aluminosilicatestructure has a porous internal cell structure on which the major axisof the pores can be from about 0.4 nanometer to about 0.65 nanometer,alternatively in the range of from about 0.65 nanometer to about 0.9nanometer. Examples of large pore zeolites may include, but are notlimited to, faujasite, zeolite Y or X, ultra-stable zeolite Y, RareEarth zeolite Y and Rare Earth ultra-stable zeolite Y. Examples ofmedium pore zeolites may include, but are not limited to, the ModerniteFramework Inverted (MFI) structural type (e.g., ZSM-5), the MTW type(e.g., ZSM-12), the TON structural type (e.g., theta) and the FERstructural type (e.g., ferrierite).

In at least one embodiment, a hydrogenation catalyst for the FCC processis a hydrogenation catalyst that is resistant to the combination of theorganic solvent and/or the solvent mixture and, if present, the acidcatalyst. For example, a hydrogenation catalyst may include aheterogeneous and/or homogeneous catalyst, such as the hydrogenationcatalyst is a homogeneous catalyst, alternatively a heterogeneouscatalyst. The hydrogenation catalyst may include a hydrogenation metalknown to be suitable for hydrogenation reactions, such as for examplenickel, iron, palladium, ruthenium, rhodium, molybdenum, cobalt, copper,iridium, platinum and gold, or mixtures thereof.

The hydrogenation catalyst including such a hydrogenation metal may besulfided. Further, sulfided hydrogenation catalysts may be used such as,for example, a catalyst based on Molybdenum sulfide, potentiallyincluding Cobalt and/or Nickel as a promotor, such as sulfidedNiMo/Al₂O₃ catalyst.

With respect to the hydrogenation catalyst being a heterogeneouscatalyst, the catalyst may include a hydrogenation metal supported on acarrier. Suitable carriers include for example carbon, alumina, titaniumdioxide, zirconium dioxide, silicon dioxide and mixtures thereof.Examples of suitable heterogeneous hydrogenation catalysts may include,but are not limited to, ruthenium, platinum or palladium supported on acarbon carrier, such as ruthenium supported on zirconium dioxide ortitanium dioxide. Any suitable form of the heterogeneous catalyst and/orcarrier used for the present process may be a mesoporous powder,granules, pellets, tablets or any extrudates, megaporous structure(e.g., honeycomb, cloth, foam, and/or mesh). The heterogeneous catalystmay be present in a FCC reactor included in a fixed bed reactor orebullated slurry bed reactor, such as in a fixed bed reactor.

With respect to the hydrogenation catalyst being a homogeneoushydrogenation catalyst, the catalyst may include an organic or inorganicsalt of a hydrogenation metal. Suitable examples of organic or inorganicsalt of a hydrogenation metal can be, but are not limited to, acetate-,acetylacetonate-, nitrate-, sulphate- or chloride-salt of palladium,platinum, nickel, cobalt, rhodium or ruthenium, such as, in at least oneembodiment, the homogeneous catalyst is an organic or inorganic acidsalt of a hydrogenation metal, where the acid is an acid already presentin the process as the acid catalyst (described above).

In at least one embodiment, a source of hydrogen may be any source ofhydrogen known to be suitable for hydrogenation purposes, which mayinclude hydrogen gas and/or hydrogen-donor (e.g., formic acid), such asthe source of hydrogen is a hydrogen gas. Hence, such hydrogen gasintroduced to the FCC reactor at a partial hydrogen pressure that can bein the range of from about 0.01 MPa to 30 MPa, such as from about 0.05MPa to about 28 MPa, such as from about 0.1 MPa to about 26 MPa, such asfrom about 0.5 MPa to about 24 MPa, such as from about 1 MPa to about 22MPa, such as from about 2 MPa to about 20 MPa, such as from about 3 MPato about 18 MPa, such as from about 4 MPa to about 16 MPa. A hydrogengas can be supplied to an FCC reactor co-currently, cross-currently orcounter-currently to the HTL oil, such as the hydrogen gas is suppliedcounter-currently to the HTL oil.

In the FCC unit, the cracking process can be carried out at any totalpressure known to be suitable for cracking processes, such as thecracking process can be carried out under a total pressure value of fromabout 10 psig to about 50 psig, such as about 15 psig (1 bar) to about30 psig (2 bar).

Additionally, during the cracking process in the FCC unit, the HTL oiland one or more hydrocarbon(s) are cracked, namely the HTL oil and oneor more hydrocarbon(s) may be converted into one or more crackedproduct(s), to produce cracked product(s), such as a biofuel product. Inat least one embodiment, the final biofuel product is eitherhydrogenated or not. Furthermore, the final cracked product can becontacted/blended with one or more component(s), such as any fueladditives (e.g., metal deactivators, corrosion inhibitors, leadscavengers, fuel dyes, and antioxidant stabilizers), to form a biofuelcomposition. Methods of the present disclosure (e.g., HTL oil +dualnozzle system) can provide improved final cracked products that do notneed to be fractionated before blending with one or more components,saving energy, time, and cost in product of biofuels. The one or morecomponents can be selected from an anti-oxidant, a corrosion inhibitor,an ashless detergent, a dehazer, a dye, a lubricity improver, a mineralfuel component, a petroleum derived gasoline, a diesel, and a kerosene.

The reaction effluent produced in the cracking process in the FCC unitmay include insoluble solid materials such as humins (also referred toas “char”) and the cracked product(s), including the processed-HTL oiland hydrocarbon(s). Moreover, the reaction effluent may include, forexample, water (expected to be in much lower amount when compare to thewater formed during fast pyrolysis), co-solvent, acid catalyst and/orhydrogenation catalyst, and/or gaseous products (e.g., hydrogen,nitrogen). In at least one embodiment, the cracking process of thepresent disclosure does not include any separation of the final crackedproduct from a reaction effluent produced in the cracking process.Hence, the reaction effluent is not forwarded to a separation section.In at least one embodiment, the final cracked product is the RIN-biofuelproduct(s).

The water produced during the cracking process may be removed bydistillation, pervaporation and/or reversed osmosis. The final crackedproduct may include hydrocarbon compounds and/or a small amount ofoxygenates, such as for example alcohols (e.g., mono- and/ordi-alcohols) and/or ketones (mono- and/or di-ketones).

In at least one embodiment, the present disclosure provides a method ofprocessing a hydrocarbons fraction (e.g., VGO) with a substituted amountof a processed-HTL oil in the presence of a catalyst resulting in asustaining and/or increasing or improving the yield of a transportationfuel, such as an increase of at least 0.2 wt % or at least 0.5 wt %,relative to the identical process on an equivalent energy or carboncontent basis of the feedstream where the petroleum fraction is notsubstituted to any other fuel feedstock. Examples of transportation fuelyield may be, but are not limited to, a LPG, a gasoline, a diesel fuel,a jet fuel, an LCO, a heating oil, a transportation fuel, and/or a powerfuel.

In at least one embodiment, the present disclosure provides a method ofprocessing a hydrocarbon fraction (e.g., VGO) with a substituted amountof a processed-HTL oil in the presence of a catalyst resulting in anincreased or improved yield of the biogenic carbon, such as an increaseof at least 0.5 wt %, such as an increased or improved yield of thebiogenic carbon of from about 0.5 wt % to 3 wt %, thus relative to theidentical process on an equivalent energy or carbon content basis of thefeedstream where the petroleum fraction is not substituted to any otherfuel feedstock. Examples of transportation fuel yield may be, but arenot limited to, an LPG, a gasoline, a diesel fuel, a jet fuel, an LCO, aheating oil, a transportation fuel, and/or a power fuel.

In at least one embodiment, a method of preparing a biofuel includesprocessing a hydrocarbon co-feed with a processed-HTL oil feedstock inthe presence of a catalyst. For example, a method of preparing a biofuelmay include providing a processed-HTL oil feedstock for processing witha hydrocarbon co-feed in the presence of a catalyst. In at least oneembodiment, a method of preparing a biofuel includes: i) processing ahydrocarbon co-feed with a processed-HTL oil feedstock in the presenceof a catalyst; and ii) optionally, adjusting/catering feed additionrates of a hydrocarbon co-feed, a processed-HTL oil feedstock, or both,to target a desirable biofuel product profile, a riser temperature, or areaction zone temperature; or iii) optionally, adjusting the FCCcatalyst to combined hydrocarbon co-feed and processed-HTL oil feedstockratio (catalyst : oil(s) ratio) to target a particular biofuel productprofile, a riser temperature, or a reaction zone temperature; where thecatalyst : oil(s) ratio can be a weight ratio or a volume ratio.

In at least one embodiment, feed nozzles that are modified for theproperties of conditioned renewable fuel feedstock and any suitablenozzles of the FCC are converted into stainless steel, or other suitablemetallurgy, and adjusted to inject HTL oil to provide an upgrade to thetraditional systems.

In at least one embodiment, the addition rate value of the HTL oil in arefinery FCC unit that may be processing a hydrocarbon fraction issufficient to provide mixing of the HTL oil with co-feed. Additionallyor alternatively, the contact time of the FCC catalyst and the HTL oilis about 1 second to about 30 seconds, such as about 2 seconds to about10 seconds.

FCC units may use steam to lift the catalyst. The steam can be used fordilution of the reaction media at a residence time control. The liftsteam can enter the FCC reactor riser from the bottom of the unit and/orthrough at least one or more nozzles on the side of the reactor. Thesenozzles may be located below, above or co-located with the feedstock(either the HTL oil feed, hydrocarbon feed or both HTL oil andhydrocarbon feed) injection point.

In at least one embodiment, a delivery system of the processed-HTL oilseparated from the hydrocarbon feedstock feed port (or assembly) forintroducing the processed-HTL oil material into an FCC unit is used. Theseparate delivery system may include transfer from storage, preheat anddeliver the processed-HTL oil to an appropriate injection point on theFCC. To ensure contact between the processed-HTL oil and the hydrocarbonfeedstock the point of introduction may be near to the hydrocarbonfeedstock injection nozzles which may be located in the downward sectionof the FCC reactor riser.

In at least one embodiment, the processed-HTL oil is introduced throughone or more atomizing nozzle(s) that may be inserted into one ormultiple steam lines and/or may be introduced into one or more recyclelift vapor line(s).

The addition rate of the processed-HTL oil may be controlled by aseparate delivery system (i.e., separate from the hydrocarbon deliverysystem) into the downward section of the FCC reactor riser. In analternate embodiment, the addition rate of the processed-HTL oil iscontrolled by a separate delivery system into one or multiple lift steamline(s). The addition rate of the processed-HTL oil may be controlled bya separate delivery system into an available port in the downwardsection of the FCC reactor riser. In a further alternate embodiment, theaddition rate of the processed-HTL oil is controlled by a separatedelivery system and introduced into one of the hydrocarbon nozzles orinjectors either separately or with the hydrocarbon feedstock, such asseparately of the hydrocarbon feedstock.

In at least one embodiment, a method of the present disclosure includes:i) producing a processed-HTL oil based feedstock; ii) introducing theprocessed-HTL oil based feedstock into a refinery system, where therefinery system conversion unit may be selected from a group includingan FCC, a coker, a field upgrader system, a lube oil refinery facility,a hydrocracker, and a hydrotreating unit; iii) and co-processing theprocessed-HTL oil based feedstock with a hydrocarbon feedstock (e.g.,VGO). For example, the method may include (i) producing theprocessed-HTL oil based feedstock, which includes a hydrothermalliquefaction conversion of biomass, and (ii) conditioning theprocessed-HTL oil based feedstock to provide introduction into the FCCrefinery system. Hence, the conditioning of the processed-HTL oil basedfeedstock may include controlling an ash content to be in a range ofbetween 0.001 wt % and 1 wt %; controlling a pH to be in a range of fromabout 5 to about 7, such as from about 5 to 6; and controlling a watercontent to be in a range between 0.05 wt % and 0.2 wt %. In at least oneembodiment, the hydrocarbon feedstock used is a VGO.

The conversion method of the present disclosure may include injectingthe processed-HTL oil feedstock into a catalytic riser of a FCC unit.For example, the processed-HTL oil feedstock may be injected upstream ofa VGO inlet port of a FCC unit, such as the processed-HTL oil feedstockmay be injected downstream of a VGO inlet port of a FCC unit, such asthe processed-HTL oil feedstock may be injected into a riser quench lineof a FCC unit, such as the processed-HTL oil feedstock may be injectedinto a second riser of a two riser FCC unit, such as the processed-HTLoil feedstock may be injected into a third riser of a three riser FCCunit.

In at least one embodiment, the system used for the conversion processincludes a production facility for producing a processed-HTL oil basedfeedstock and a refinery system, where the refinery system may beselected from a conversion unit including a FCC, a coker, a fieldupgrader system, a lube oil refinery facility, a hydrocracker, and ahydrotreating unit, where the processed-HTL oil based feedstock may beintroduced into the refinery system, and the HTL oil based feedstock maybe co-processed with a hydrocarbon feedstock in the refinery system.

Regenerating Catalyst

In at least one embodiment, the catalytic cracking process includes: i)an FCC process including contacting the HTL oil, the hydrocarbons, andan FCC catalyst at a temperature of from about 400° C. to about 700° C.,to produce one or more cracked products and a spent (“deactivated”) FCCcatalyst; ii) a separation process including separating one or more ofthe cracked products from the spent FCC catalyst; iii) a regenerationprocess including regenerating spent FCC catalyst to produce aregenerated FCC catalyst, heat and carbon dioxide; and a recyclingprocess including recycling the regenerated FCC catalyst to the FCCprocess.

The separation process including separating one or more of the crackedproducts from the spent FCC catalyst can be carried out using one ormore cyclone separators and/or one or more swirl tubes. Suitable methodsof carrying out the separation process are described in Fluid CatalyticCracking; Design, Operation, and Troubleshooting of FCC Facilities byReza Sadeghbeigi, published by Gulf Publishing Company, Houston Tex.,1995, pages 219 to 223, and Fluid Catalytic Cracking technology andoperations, by Joseph W. Wilson, published by PennWell PublishingCompany, 1997, chapter 3, pages 104 to 120, and chapter 6, pages 186 to194, incorporated herein by reference.

Furthermore, the separation process may include a stripping process suchas the spent FCC catalyst may be stripped to recover the productsabsorbed on the spent FCC catalyst before the regeneration process. Therecovered products may be recycled and added to a stream including oneor more cracked products obtained from the catalytic cracking process.

In at least one embodiment, the regeneration process includes contactingthe spent FCC catalyst with an oxygen containing gas in a regenerator,in order to produce a regenerated FCC catalyst, heat and carbon dioxide.The catalyst activity can be restored during the regeneration cokeprocess where the coke that can be deposited on the catalyst, as aresult of the FCC reaction, is burned off.

Additionally, the oxygen containing gas may be any suitable oxygencontaining gas for use in a regenerator, such as air or oxygen-enrichedair (OEA). The term “oxygen enriched air” refers to air including about20 vol % oxygen or greater, such as air including about 25 vol % oxygenor greater, such as air including about 30 vol % oxygen or greater,based on the total volume of air.

The heat produced in the exothermic regeneration process can be used tosupply energy for the endothermic catalytic cracking process. Moreover,the heat produced in the exothermic regeneration process can be used toheat water and/or generate steam. The steam can be used elsewhere in theFCC refinery, such as a lift gas in a riser reactor.

The regenerated FCC catalyst can be recycled back to the FCC process. Inat least one embodiment, a side stream of make-up FCC catalyst is addedto the recycle stream to make-up for loss of FCC catalyst in thereaction zone and regenerator.

Cracked Products and Compositions

The process of the present disclosure provides one or more crackedproduct(s). At this point of the process, there is no fractionation ofany of the cracked product(s) produced. Hence, there is no separationprocess of the cracked product(s) with the blend components (RFOs andhydrocarbons) if present. Such simplified, environmentally-friendly,time- and cost-efficient FCC process enables access to the desirablebiofuel with RIN credits, yet with grade quality (e.g., lowconcentration of sulfur content of from about 0.1 wt % to 2.5 wt % andheavy metals). Hence, the one or more cracked product(s) derivedtherefrom can conveniently be used directly as a biofuel component. Asused herein “grade quality” refers to a low to moderate level of sulfur(e.g., from 0.5 wt % to 2.5 wt %) and low to moderate level of heavymetals (e.g., vanadium and nickel).

In at least one embodiment, a cracked product may conveniently beblended with one or more other components to produce a biofuelcomposition. Examples of such one or more other components may includeany additives such as anti-oxidants, corrosion inhibitors, ashlessdetergents, dehazers, dyes, lubricity improvers and/or mineral fuelcomponents, but also conventional petroleum derived gasoline, dieseland/or kerosene. A biofuel composition can include one or more othercomponents at an additive content of from about 0.001 wt % to about 30wt % of any additives, such as from about 0.01 wt % to about 10 wt %,such as from about 0.1 wt % to about 3wt %, based on the weight of thebiofuel composition.

In at least one embodiment, a biofuel formed after an FCC processincludes an FCC product composition derived from catalytic contact of afeedstock including an HTL oil, such as a biofuel derived from ahydrocarbon co-feed and an HTL oil feedstock, such as a biofuel derivedfrom about 50 wt % to about 99.99 wt %, such as from about 55 wt % toabout 99.5 wt %, such as from about 60 wt % to about 99 wt %, such asfrom about 65 wt % to about 90 wt %, such as from about 70 wt % to about90 wt % of a hydrocarbon co-feed, and from about 0.01 wt % to about 50wt %, such as from about 0.5 wt % to about 45 wt %, such as from about 1wt % to about 40 wt %, such as from about 10 wt % to about 35 wt %, suchas such as from about 10 wt % to about 30 wt % of an HTL oil feedstock,or a biofuel derived from 50 vol % to about 99.99 vol %, such as fromabout 55 vol % to about 99.5 vol %, such as from about 60 vol % to about99 vol %, such as from about 65 vol % to about 90 vol %, such as fromabout 70 vol % to about 90 vol % of a hydrocarbon co-feed, and fromabout 0.01 vol % to about 50 vol %, such as from about 0.5 vol % toabout 45 vol %, such as from about 1 vol % to about 40 vol %, such asfrom about 10 vol % to about 35 vol %, such as from about 10 vol % toabout 30 vol % of an HTL oil feedstock.

EXAMPLES

Table 1 illustrates comparative results obtained from conventional datafor fast pyrolysis versus HTL of cellulosic material. When pyrolysis ofbiomass was performed by fast pyrolysis at an operating temperature offrom 450° C. to 500° C., an operating pressure of 1 atm, and at a veryshort residence time (of less than a second), without the presence ofcatalyst, a thermally unstable oil was produced with high contents ofwater (25%) and oxygenates (38%). Fast pyrolysis produced an oilcontaining very reactive species (e.g., oxygenates), which is an issuefor fuel storage and transportation. However, with HTL that requiredlower operating temperature (350° C.), longer residence time (5 minutesto 30 minutes), and higher pressure (150 atm to 250 atm, such as 200atm), produced an oil that was more thermally stable, with less waterand oxygenates contents (5% and 12%, respectively). This comparativeexperiment and the associated comparative data in Table 1 were providedin Elliott, D.C., et al. (Sep. 2, 2014), Comparative Analysis of FastPyrolysis and Hydrothermal Liquefaction as Routes for Biomass Conversionto Liquid Hydrocarbon Fuels, PowerPoint slides presented at theSymposium on Thermal and Catalytic Sciences for Biofuels and BiobasedProducts, TCS 2014 (Denver, Colo.).

TABLE 1 Fast Pyrolysis Hydrothermal Liquefaction Conditions FeedstockDry Biomass Wet Biomass Operating Temperature 450° C.-500° C. 350° C.Operating Pressure 1 atm 200 atm Residence Time <1 sec 5 to 30 minCarbon Yield to Bio-oil 70% 35% Oil Product Quality Oxygen Content, Dry38% 12% Basis Water Content 25%  5% Thermal Stability less more

Table 2 illustrates prophetic yields developed for the use of HTL oilblended with hydrocarbon feedstock (e.g., gasoline, diesel) in the FCCunit. When a petroleum fraction of VGO is mixed with a substitutedamount of an HTL oil (5%) in the presence of a catalyst, the quality ofthe gasoline or the diesel fuel is not negatively affected. The yield ofgasoline (and diesel) remains overall the same. The gasoline (or diesel)yield can also be represented in terms of the amount of carbon in thefeedstock that may be converted to gasoline (or diesel). Surprisingly,the yields of biogenic carbon of gasoline and diesel increase (2% and1%, respectively). These yields suggest that more carbon in the VGO maybe going to gasoline (and diesel) production than would otherwise be thecase without the addition of the HTL oil in the blend. HTL oil may besynergistically affecting either the cracking chemistry or catalystactivity in favor of the gasoline (or diesel) product. These propheticresults demonstrate that combining a hydrocarbon fuel with an HTL oilvia a simple process for the production of cost- and time-efficientgeneration of biofuels having RIN credits, i.e., the cellulosic RINcredits.

TABLE 2 Biogenic Carbon VGO VGO + 5% HTL (% estimate) C2 3 3 C3/C4 1211.8 Gasoline 50 49.2 2% Ico Diesel 20 20 1% Bottoms 9 9 Coke 6 6 Water0.2 CO + CO₂ 0.8 Total 100 100 Conversion 71 71

Subsequent to the above prophetic example, actual experiments were runon an HTL sample. Table 3 below summarizes two data sets comparing VGOonly and VGO +5% HTL. The two data sets have different operatingconditions. Results are similar to those predicted in the propheticexample. Note that biogenic carbon was not measured, but the assumptionsof the biogenic carbon shown in Table 2 would be expected to apply tothe experimental data. Also, water and CO/CO₂ results in the actualexperiments were unavailable.

TABLE 3 Data Set I Data Set II Exp. # 273 287 275 289 Cat/Oil 6.12 6.126.12 4.7 Crack. Temp. 970° F. 1010° F. 900° F. 900° F. Feed VGO VGO +VGO VGO + 5% HTL 5% HTL C2 1.06 1.42 0.63 0.7 C3/C4 15.73 17.2 11.9712.48 Gasoline 42.1 39.96 41.8 39.09 Ico Diesel 21.266 22.2 24.16 25.68Bottoms 15.1 13.7 16.97 16.49 Coke 3.77 4.31 3.81 4.98 Water dataunavailable CO + CO2 data unavailable Total 99.026 98.79 99.34 99.42Conversion 63.64 64.1 58.87 57.83

Overall, processes of the present disclosure can provide thermallystable biofuel compositions providing conversion of a hydrocarbonfeedstock using an HTL oil, thus with less water and oxygenates content.Processes of the present disclosure can provide biofuel compositionswithout any separation (e.g., fractionation) of the cracked product(s)after FCC providing additional time-, energy- and cost-efficiency. TheFCC process can be performed using a system of at least two or moreinjection nozzles coupled with the FCC unit, which promotes betterblending of the HTL and hydrocarbon oils (and ultimately crackedproduct(s)) by increasing the gas/oil dispersion, providing additionaltime-, energy- and cost-efficiency.

The phrases, unless otherwise specified, “consists essentially of” and“consisting essentially of” do not exclude the presence of otherprocesses, elements, or materials, whether or not, specificallymentioned in this specification, so long as such processes, elements, ormaterials, do not affect the basic and novel characteristics of thepresent disclosure, additionally, they do not exclude impurities andvariances normally associated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the present disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including”. Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of” “consisting of,” “selected from thegroup of consisting of” or “is” preceding the recitation of thecomposition, element, or elements and vice versa.

While the present disclosure has been described with respect to a numberof embodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the present disclosure.

1. A method for forming a biofuel composition, comprising: introducingseparately a hydrothermal liquefaction (HTL) oil derived from cellulosicmaterial, a hydrocarbon co-feed and a cracking catalyst into a crackingunit to form a mixture; and processing the mixture at a temperature ofabout 350° C. or greater to form a cracked product.
 2. The method ofclaim 1, wherein the cracked product is not fractionated.
 3. The methodof claim 1, wherein the cracking unit comprises two or more injectionnozzles coupled with the cracking unit.
 4. The method of claim 1,further comprising blending the cracked product with one or more fueladditive components, wherein the biofuel composition comprises one ormore fuel additive components.
 5. The method of claim 4, wherein the oneor more fuel additive components are selected from an anti-oxidant, acorrosion inhibitor, an ashless detergent, a dehazer, a dye, a lubricityimprover, a mineral fuel component, a petroleum derived gasoline, adiesel, and a kerosene.
 6. The method of claim 1, wherein the biofuelcomposition has a water content of about 5% or less.
 7. The method ofclaim 1, further comprising introducing the hydrocarbon co-feed into thecracking unit using a first nozzle and introducing the HTL oil into thecracking unit using a second nozzle.
 8. The method of claim 1, whereinthe hydrocarbon co-feed comprises one or more of a straight run(atmospheric) gas oil, a flashed distillate, a vacuum gas oil, a lightcycle oil, a heavy cycle oil, a hydrowax, a coker gas oil, a gasoline, anaphtha, a diesel, a kerosene, an atmospheric residue, a vacuum residue,or a combination thereof.
 9. The method of claim 1, wherein thehydrocarbon co-feed is a vacuum gas oil.
 10. The method of claim 8,wherein the ratio of the amount of cracking catalyst to the total amountof hydrothermal liquefaction oil and hydrocarbon co-feed is from about2/1 to about 10/1.
 11. The method of claim 1, further comprisingintroducing a catalyst additive to the cracking unit.
 12. A method forforming a biofuel composition, comprising: introducing a cellulosicmaterial to a solvent in the presence of a catalyst at a temperature ofabout 350° C. or greater and an operating pressure of about 200 atm orgreater to form a first liquefied product; hydrotreating the firstliquefied product with a source of hydrogen in the presence of ahydrotreatment catalyst to produce a second liquefied product;introducing the second liquefied product and a cracking catalyst to afluidized catalytic cracking unit at a temperature of about 350° C. orgreater to form a cracked product; hydrotreating the cracked productwith a source of hydrogen in the presence of a hydrotreatment catalystto produce a hydrotreated cracked product; and blending the hydrotreatedcracked product with one or more fuel additive components to form abiofuel composition.
 13. The method of claim 12, wherein the crackedproduct is not fractionated before blending with the one or more fueladditive components.
 14. The method of claim 12, wherein the one or morefuel additive components are selected from an anti-oxidant, a corrosioninhibitor, an ashless detergent, a dehazer, a dye, a lubricity improver,a mineral fuel component, a petroleum derived gasoline, a diesel, and akerosene.
 15. The method of claim 12, wherein the biofuel compositioncomprises the one or more fuel additive components from about 0.1 wt %to about 3 wt %, based on the total weight of the biofuel composition.16. The method of claim 12, wherein the biofuel composition has a watercontent of about 5% or less.
 17. The method of claim 12, furthercomprising introducing a hydrocarbon co-feed into the fluidizedcatalytic cracking unit, wherein the liquefied product is introducedusing a first nozzle to the fluidized catalytic cracking unit and thehydrocarbon co-feed is introduced using a second nozzle to the fluidizedcatalytic cracking unit.
 18. The method of claim 17, wherein thehydrocarbon co-feed comprises one or more of a straight run(atmospheric) gas oil, a flashed distillate, a vacuum gas oil, a lightcycle oil, a heavy cycle oil, a hydrowax, a coker gas oil, a gasoline, anaphtha, a diesel, a kerosene, an atmospheric residue, a vacuum residue,or a combination thereof.
 19. The method of claim 17, wherein thehydrocarbon co-feed is a vacuum gas oil.
 20. The method of claim 12,wherein the solvent is a petroleum oil.
 21. The method of claim 12,wherein hydrotreating the first liquefied product comprises introducinga hydrogen source and a hydrogenation catalyst to the liquefaction unitat a temperature of about 150° C. or greater.
 22. The method of claim12, wherein the first and/or second liquefied product comprises one ormore of gamma-valerolactone, levulinic acid, tetrahydrofufuryl,tetrahydropyranyl, furfural hydroxymethylfurfural, mono-alcohol,di-alcohol, mono-ketone, di-ketone, guaiacol, or syringol.
 23. Themethod of claim 12, wherein the ratio of the amount of cracking catalystto the amount of second liquefied product is from about 2/1 to about10/1.
 24. The method of claim 18, wherein the ratio of the amount ofcracking catalyst to the total amount of second liquefied product andhydrocarbon co-feed is from about 2/1 to about 10/1.
 25. The method ofclaim 12, further comprising introducing a catalyst additive to thefluidized catalytic cracking unit.